JP5155845B2 - Structure estimation device, structure estimation method, structure estimation program, and recording medium - Google Patents

Description

  The present invention relates to a structure estimation apparatus, a structure estimation method, a structure estimation program, and a computer-readable recording medium recording the structure estimation program for estimating the structure of a transition metal complex in an organic solution.

  Examples of a method for estimating the structure of a transition metal complex used in an organic synthesis reaction in the reaction system include, for example, nuclear magnetic resonance spectrum (hereinafter referred to as NMR) and electron spin resonance (EPR). ) Etc. are used.

On the other hand, for a transition metal complex whose structure is known (that is, stable), an ultraviolet-visible absorption spectrum (hereinafter sometimes referred to as a TD-DFT method) is used. In the following, it is known that UV spectrum may be estimated (for example, see Non-Patent Document 1).
VIAvdeev and GMZhidomirov, Journal of Structural Chemistry, Vol.46, No.4, P577-590 (2005)

  However, NMR cannot be used to estimate the structure of organometallic complexes exhibiting magnetism. Also, EPR cannot be used for structure estimation of organometallic complexes that do not have lone electrons. Therefore, both NMR and EPR are not practical structure estimation methods.

  In addition, since it is difficult to crystallize unstable transition metal complexes existing in organic synthesis reaction systems, the structure cannot be determined using UV spectra in the same manner as stable transition metal complexes. .

  Moreover, since the UV spectrum is monotonous, it has not been used for estimating the structure of unstable transition metal complexes present in the organic synthesis reaction system.

  The present invention has been made to solve the above-described problems, and its purpose is to provide a structure estimation apparatus and structure estimation capable of estimating the structure of an unstable transition metal complex present in an organic synthesis reaction system. It is to provide a method.

  In order to solve the above problems, a structure estimation apparatus according to the present invention is a structure estimation apparatus that estimates the structure of a transition metal complex that catalyzes a chemical reaction in a reaction system including an organic solvent, the transition metal complex, An acquisition means for acquiring specific information for specifying each of the organic solvent and at least one target compound to be a catalyst of the transition metal complex, a transition metal complex indicated by the specific information acquired by the acquisition means, an organic solvent, and Candidate determining means for determining a plurality of transition metal complexes that may be generated by mixing the target compounds as transition metal complex candidates, and an ultraviolet-visible absorption spectrum of at least a part of the transition metal complex candidates determined by the candidate determining means Spectrum estimation means for estimating the estimated UV-visible absorption spectrum estimated by the spectrum estimation means, and the specific information Compared with the actual UV-visible absorption spectrum obtained by actually measuring the UV-visible absorption spectrum of the mixture of the transition metal complex, organic solvent and target compound shown, an estimated UV-visible absorption spectrum similar to the actual UV-visible absorption spectrum is obtained. And a comparing means for specifying.

  A structure estimation method according to the present invention is a structure estimation method in a structure estimation apparatus for estimating a structure of a transition metal complex that catalyzes a chemical reaction in a reaction system including an organic solvent, the transition metal complex, the organic solvent, and An acquisition process for acquiring specific information for identifying at least one target compound to be a catalyst target of the transition metal complex, and a transition metal complex, an organic solvent, and the target compound indicated by the specific information acquired in the acquisition process are mixed. A candidate determination step for determining a plurality of transition metal complexes that may be generated as a transition metal complex candidate, and estimating an ultraviolet-visible absorption spectrum of at least a part of the transition metal complex candidates determined in the candidate determination step Spectral estimation process and estimated UV-visible absorption spectrum estimated in the above spectral estimation process Comparison with the actual UV-visible absorption spectrum obtained by actually measuring the UV-visible absorption spectrum of the mixture of the transition metal complex, organic solvent and target compound indicated by the above specific information, and estimation similar to the actual UV-visible absorption spectrum And a comparison step for specifying an ultraviolet-visible absorption spectrum.

  According to said structure, an acquisition means acquires the specific information which each specifies a transition metal complex, an organic solvent, and at least 1 object compound, and a candidate determination means is a transition metal complex which an identification information shows, an organic solvent, A plurality of transition metal complexes that may be generated by mixing the target compound and the target compound are determined as transition metal complex candidates.

  The spectrum estimating means estimates at least a part of the UV-visible absorption spectrum of the transition metal complex candidate determined by the candidate determining means, and the comparing means calculates the estimated UV-visible absorption spectrum estimated by the spectrum estimating means and the actually measured UV-visible absorption spectrum. And an estimated UV-visible absorption spectrum close to the actually measured UV-visible absorption spectrum is specified.

  Therefore, the structure of a transition metal complex that cannot be crystallized because it is unstable in an organic synthesis reaction system can be easily estimated. Therefore, since it can contribute to the development of an efficient catalyst, it is industrially advantageous.

  Note that the criterion for determining whether the estimated ultraviolet-visible absorption spectrum is similar to the actually measured ultraviolet-visible absorption spectrum may be set as appropriate by the user. And a comparison means should just specify the estimated ultraviolet visible absorption spectrum which satisfy | fills the predetermined criteria for determining whether an estimated ultraviolet visible absorption spectrum and the measurement ultraviolet visible absorption spectrum are similar.

  The above criteria are, for example, the number of peaks in the estimated UV-visible absorption spectrum, the peak wavelength, the distance (wavelength) between peaks when there are multiple peaks, or the ratio of peak intensities when there are multiple peaks. Is a criterion of whether it agrees with that of the actually measured UV-visible absorption spectrum.

  In addition, it is ideal that the comparison unit specifies one estimated ultraviolet-visible absorption spectrum that is most similar to the actually measured ultraviolet-visible absorption spectrum. The estimated UV-visible absorption spectrum may be output as a comparison result.

  The structure estimation apparatus includes a first ligand included in the transition metal complex indicated by the specific information acquired by the acquisition unit, a second ligand that may be generated from the target compound indicated by the specific information, and It further comprises a ligand specifying means for specifying the post-desorption compound after the second ligand is desorbed from the target compound, and the candidate determination means includes the organic solvent, the target compound, and the At least one substance selected from the group consisting of the first and second ligands specified by the ligand specifying means and the compound after elimination is distributed to the transition metal contained in the transition metal complex indicated by the specific information. It is preferable that a plurality of transition metal complexes generated by binding or bonding are determined as transition metal complex candidates.

  According to the above configuration, the ligand identifying means identifies the ligand that may be generated from the transition metal complex and the target compound, and the compound after desorption after the ligand is desorbed from the target compound. . Candidate determination means include an organic solvent indicated by specific information, a target compound, a first or second ligand specified by the ligand specifying means, or a compound after elimination, or a combination thereof coordinated or bonded to the transition metal. A plurality of transition metal complexes that may be generated as a result are determined as transition metal complex candidates.

  Therefore, complex candidates can be determined more comprehensively, and the accuracy of estimating the structure of the transition metal complex can be improved.

  When there are a plurality of estimated UV-visible absorption spectra specified by the comparison means, the structure estimation device is chemically unstable from a plurality of transition metal complex candidates from which the estimated UV-visible absorption spectra are estimated. It is preferable to further include candidate selection means for removing transition metal complex candidates.

  According to the above configuration, the candidate selection means, from the plurality of transition metal complex candidates showing the plurality of estimated UV-visible absorption spectra specified by the comparison means, is unlikely to exist and is a chemically unstable transition metal complex. Candidates are removed.

  Therefore, even when the number of transition metal complex candidates cannot be narrowed down to one by comparison of ultraviolet-visible absorption spectra, the transition metal complex candidates can be further narrowed down.

  The structure estimation device further includes candidate selection means for removing chemically unstable transition metal complex candidates from the transition metal complex candidates determined by the candidate determination means, and the spectrum estimation means is selected by the candidate selection means. It is preferable to estimate the ultraviolet-visible absorption spectrum of each of the narrowed transition metal complex candidates.

  According to the above configuration, the candidate selection unit removes the chemically unstable transition metal complex candidate that is unlikely to exist from the transition metal complex candidate determined by the candidate determination unit, and the spectrum estimation unit includes: The UV-visible absorption spectra of the transition metal complex candidates narrowed down by the candidate selection means are estimated.

  Therefore, since the transition metal complex candidates can be narrowed down before estimating the UV-visible absorption spectrum, the amount of processing for estimating the UV-visible absorption spectrum can be reduced.

  The structure estimation apparatus further includes structure optimization means for determining a chemically stable structure of the transition metal complex candidate determined by the candidate determination means by quantum chemical calculation, and the spectrum estimation means includes the structure It is preferable to estimate the ultraviolet-visible absorption spectrum of the structure determined by the optimization means.

  According to the above configuration, the structure optimization means determines the optimum structure of the transition metal complex candidate determined by the candidate determination means by quantum chemical calculation, and the spectrum estimation means determines the optimum structure determined by the structure optimization means. Estimate the UV-visible absorption spectrum.

  Therefore, the ultraviolet-visible absorption spectrum can be estimated based on the structure of the transition metal complex candidate that is most likely to exist, and the accuracy of estimating the structure of the transition metal complex can be improved.

  The spectrum estimation means preferably calculates the estimated ultraviolet-visible absorption spectrum by a time-dependent density functional method.

  In addition to the time-dependent density functional method, the CIS method and the ZINDO (Zerner's Intermediate Neglect of Differential Overlap) method are known as methods for estimating the UV-visible absorption spectrum. When calculating a transition metal complex, The time-dependent density functional theory can be estimated with the highest accuracy. Therefore, with the above configuration, the structure of the transition metal complex can be estimated with higher accuracy.

  The candidate determination means preferably acquires information for determining at least one of transition metal complex candidates including Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, or Ag.

  With the above configuration, transition metal complex candidates including Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, or Ag, which are unstable transition metal complexes that are difficult to estimate by NMR, are obtained. And the structure of these transition metal complexes can be deduced.

  Preferably, the structure optimization means determines a chemically most stable structure for each of a plurality of electronic states that can be taken by the transition metal complex candidate.

  With the above configuration, the electronic state is taken into account when determining the structure of the transition metal complex candidate. Thereby, the structure of the transition metal complex can be estimated with higher accuracy.

  The structure optimization means calculates the energy value of the transition metal complex candidate for each of the electronic states, and the structure estimation device uses the energy value calculated by the structure optimization means as the transition metal complex candidate. It is preferable to further include an electronic state selection unit that selects the transition metal complex candidate in the electronic state having the smallest energy value as an estimation target of the UV-visible absorption spectrum by the spectrum estimation unit.

  According to said structure, a structure optimization means calculates the value of the energy of the said transition metal complex candidate about each of the electronic state which a transfer metal complex candidate can take. The electronic state selection means compares the energy value calculated by the structure optimization means for each transition metal complex candidate, and the transition metal complex candidate having the smallest energy value is used as an estimation target of the spectrum estimation means. select.

  Therefore, a chemically stable transition metal complex candidate can be identified using the electronic state of the transition metal complex candidate as an index, and the transition metal complex candidates can be narrowed down with high accuracy.

  Further, a structure estimation program for operating the structure estimation apparatus, a structure estimation program for causing a computer to function as each of the above-described means, and a computer-readable recording medium recording the structure estimation program are also included in the technical scope of the present invention. include.

  As described above, the structure estimation apparatus according to the present invention obtains specific information for identifying each of a transition metal complex, an organic solvent, and at least one target compound to be a catalyst of the transition metal complex, Candidate determination means for determining a plurality of transition metal complexes that may be generated by mixing the transition metal complex, the organic solvent, and the target compound indicated by the specific information acquired by the acquisition means as transition metal complex candidates, and the above candidate determination Spectrum estimation means for estimating at least part of the UV-visible absorption spectrum of the transition metal complex candidate determined by the means, estimated UV-visible absorption spectrum estimated by the spectrum estimation means, transition metal complex, organic solvent indicated by the specific information UV-Visation obtained by actually measuring the UV-Vis absorption spectrum of the mixture of the target compound Comparing the yield spectrum, a configuration and a comparison means for identifying estimated ultraviolet-visible absorption spectrum similar to the measured ultraviolet-visible absorption spectrum.

  As described above, the structure estimation method according to the present invention acquires the specific information for specifying each of the transition metal complex, the organic solvent, and at least one target compound to be the catalyst of the transition metal complex, and the above acquisition. Candidate determination step for determining a plurality of transition metal complexes that may be generated by mixing the transition metal complex, the organic solvent, and the target compound indicated by the specific information acquired in the process as transition metal complex candidates, and the above candidate determination A spectrum estimation step for estimating at least part of the UV-visible absorption spectrum of the transition metal complex candidate determined in the step, an estimated UV-visible absorption spectrum estimated in the spectrum estimation step, and a transition metal complex indicated by the specific information, By actually measuring the UV-visible absorption spectrum of a mixture of organic solvent and target compound It was compared with the measured ultraviolet-visible absorption spectrum, a configuration including a comparison step of identifying the estimated ultraviolet-visible absorption spectrum similar to the measured ultraviolet-visible absorption spectrum.

  Therefore, even if the transition metal complex cannot be crystallized because it is unstable in the organic synthesis reaction system, the structure can be easily estimated.

  As described above, although the UV spectrum is a monotonous spectrum, since the absorption derived from the metal-to-ligand charge transfer characteristic of the transition metal complex is observed, the present inventor can easily transition using the UV spectrum. We thought that the structure of the metal complex could be estimated.

  Therefore, first, quantum chemistry calculations are performed for all the intermediates that may be configured in the reaction system, the respective structures are optimized, and the UV spectra of the obtained optimal structures are estimated by the TD-DFT method. And corrections were made as necessary. If the UV spectrum of this optimal structure is matched with the actually measured UV spectrum separately measured, the structure of the transition metal complex in the reaction system is estimated.

  Then, the structure of the transition metal complex in the reaction system can be easily estimated by automatically performing the above-described quantum chemical calculation, UV spectrum estimation by the TD-DFT method, and matching with the measured UV spectrum. The headline, the present invention has been reached.

  Before specifically describing the embodiment of the structure estimation apparatus of the present invention, the principle of accumulation of reaction intermediates and the principle of detecting metal complexes in a reaction system using a metal complex catalyst will be described.

(Principle of reaction intermediate accumulation)
When the reaction proceeds in the reaction solution by the transition metal complex catalyst, the product is obtained through several reaction transition states. In general, there are a plurality of reaction intermediates having different structures from the reactants and products (see FIG. 2).

  Between the activation energy and the reaction rate constant, the relationship of the Arrhenius rate equation shown in the following equation (1) is known.

  In the above formula (1), k represents a reaction rate constant, A represents a frequency factor (positive constant), ΔE represents activation energy, R represents a gas constant (8.314 J / K mol), and T represents a reaction temperature. This equation means that as the activation energy increases, the reaction rate constant k decreases and the reaction rate decreases.

Among the plurality of transition states, the reaction rate of the transition state (TS2 in FIG. 2) having the highest activation energy, that is, the maximum ΔE in equation (1) (ΔE _{2 in} FIG. 2) is the slowest, and its stage (rate-limiting) It is surmised that the intermediate (GS2 in FIG. 2) prior to the stage) is present in the system at the only high concentration.

  As the reaction proceeds over time, the reactant is converted into a product, and at the same time, the intermediate disappears from the reaction system. Capturing is possible if the activation energy is reasonably high and the time (lifetime) present in the intermediate reaction system is longer than the measurement limit.

  On the other hand, when the activation energy in the rate-limiting step is low, the reaction proceeds fast and is instantaneously converted into a product, and it may be difficult to capture the intermediate by a spectroscopic method.

  However, since the reaction rate can be delayed by lowering the reaction temperature T from the formula (1), even if it is difficult to capture the intermediate at the normal reaction temperature, it can be captured by adjusting the measurement conditions. It will be possible.

  In addition, when there are a plurality of rate-determining steps having the same activation energy in the reaction system, it is expected that the absorption shifts with time when measured by a UV spectrum or the like. In this case, it is considered that the spectra derived from the individual intermediates can be individually captured by adjusting the measurement conditions at the reaction temperature T as described above.

However, when the activation energy (ΔE _{1 in} FIG. 2) between the intermediate before the rate-limiting step (GS2 in FIG. 2) and the intermediate in the previous step (GS1 in FIG. 2) is low, two intermediates (see FIG. 2 GS1, GS2) are likely to coexist in a state close to equilibrium.

  Even in this case, if the energy of the two intermediates (GS1 and GS2 in FIG. 2) has a difference of about 3 kcal / mol, the existence ratio is greatly biased to one side according to the Boltzmann distribution. For example, the abundance ratio when the energy difference is 3 kcal / mol standard state is 99.6 / 0.4. If the intermediate before the rate-limiting step is in equilibrium with other intermediates and there is almost no energy difference between the intermediates, multiple intermediate complexes may be present in the reaction solution at the same concentration. As will be described later, in the present invention, the structure of a plurality of intermediate complexes can be estimated using the sum of estimated spectra.

  Since the absorption range of the UV spectrum is greatly different between the product and the transition metal complex, if a spectrum different from that of the catalyst alone, the reactant, or the product is observed in the reaction system, the spectrum is the reaction intermediate before the rate-limiting step. It is reasonable to think of the spectrum as a single body.

(Principle of metal complex detection)
The metal complex that exists relatively stably in the reaction system is derived from characteristic absorption called MLCT (Metal to ligand Charge Transfer). Even if there are many organic compounds broken from the complex in the system, they are different from the absorption wavelength derived from the organometallic complex, so they do not overlap and can be distinguished from the organic compounds. This is shown from measured data and TD-DFT calculation results.

  It was found by examining the TD-DFT calculation that the metal complex has a specific absorption waveform depending on the type and number of organic compounds and ligands bonded, and the type and number of solvents. The absorption waveform is monotonous compared to NMR and IR, but can be identified because it differs depending on the structure of the complex.

  The metal complex structure candidates can be efficiently narrowed down further by using the heat of reaction by theoretical calculation for the estimation of the complex structure using the TD-DFT calculation and the measured spectrum.

  All metal complex structures that can be assumed to exist in solution are assembled, and structural optimization is performed by theoretical calculation.

[Embodiment 1]
(Configuration of structure estimation apparatus 1)
Next, an embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a schematic diagram showing the configuration of the structure estimation apparatus 1.

  As shown in FIG. 1, the structure estimation apparatus 1 includes a control unit 20, an input unit 11, an output unit 12, and a storage unit 13.

  The input unit 11 is for a user to input specific information for specifying a transition metal complex, an organic solvent in a reaction system including the transition metal complex, and a reactant (target compound) that is a catalyst target of the transition metal complex. An input device, for example, a keyboard, a mouse, or a touch panel.

  The output unit 12 is an output device for outputting information such as the structure of the transition metal complex estimated by the structure estimation device 1, and is, for example, a display device such as a liquid crystal display or a printer.

  The control unit 20 controls the structure estimation apparatus 1 and includes an acquisition unit (acquisition unit) 2, a ligand identification unit (ligand identification unit) 3, a candidate determination unit (candidate determination unit) 4, and three-dimensional. A structure determination unit 5, a structure optimization unit 6, a spectrum estimation unit (spectrum estimation unit) 7, an absorption curve creation unit 8, a comparison unit (comparison unit) 9, and a candidate selection unit (candidate selection unit) 10 are provided.

(Acquisition part 2)
The acquisition unit 2 acquires the specific information via the input unit 11 and outputs the acquired specific information to the ligand specification unit 3 and the candidate determination unit 4.

(Ligand specific part 3)
The ligand identification unit 3 may be generated from a ligand (first ligand) that the transition metal complex indicated by the specific information acquired by the acquisition unit 2 has in advance, or a reactant indicated by the specific information. A certain ligand (second ligand) and a post-desorption reactant (post-desorption compound) that is a compound after the second ligand is desorbed from the reactant are identified.

  As a method for identifying the first and second ligands and the reactant after elimination, the ligand generated from the reactant, the ligand resulting from the transition metal complex, and the ligand is eliminated from the reactant. Information necessary for specifying the post-desorption reactant generated by the above is stored in the storage unit 13 as a structure data file 13a, and the ligand specifying unit 3 refers to the structure data file 13a so that the first The second ligand and the reaction product after elimination may be specified.

  With respect to the reactant, a structure (e.g., a leaving group) that is easily cleaved by the reactant is cleaved, and the leaving group (i.e., the second ligand) and the reactant cleaved from the leaving group (the reactant after elimination) ). Examples of the leaving group include a halogen atom, a tosyl group, a mesyl group, a triflate group, a silyl group, a silyloxy group, and a hydrogen atom. When the reactant is desorbed, any charge after desorption is an anion.

  In addition, there may be a plurality of types of the first and second ligands. A ligand has all the compounds which have a hetero atom which can coordinate to a transition metal, and a structure change and deterioration do not occur in a reaction system.

(Candidate determination unit 4)
The candidate determination unit 4 is a group consisting of organic solvent molecules, reactants, the first and second ligands identified by the ligand identification unit 3 and the post-desorption reactants indicated by the specific information acquired by the acquisition unit 2. A plurality of transition metal complexes generated by coordinating or binding to a transition metal included in the transition metal complex indicated by the specific information is selected as a plurality of transition metal complex candidates (hereinafter abbreviated as complex candidates). decide.

  For example, the candidate determination unit 4 may coordinate the first and second ligands, reactants, post-elimination reactants, and / or solvent molecules described above from 1 to 6 coordinates on the transition metal. Define all possible connection relationships.

  The candidate determination unit 4 creates a binding table 14 indicating the above binding relationship (in other words, the structure of each complex candidate) and stores it in the storage unit 13. Each complex candidate shown in the binding table 14 is given an identification number (ID). Details of the processing in the candidate determination unit 4 will be described later.

(3D structure determination unit 5)
The three-dimensional structure determination unit 5 represents the structure of the complex candidate determined by the candidate determination unit 4 as three-dimensional coordinates (initial three-dimensional coordinates) for quantum chemical calculation. The method for generating the initial three-dimensional coordinates in the three-dimensional structure determining unit 5 may be a known one, and the commercially available software for the three-dimensional structure determining unit 5 is CORINA (www.molecular-networks.com) or CONCORD (www.tripos .com). If there is a possibility of taking several conformations, all structures are generated.

(Structure optimization unit 6)
The structure optimization unit 6 calculates the optimal structure (chemically most stable structure) of the structure determined by the three-dimensional structure determination unit 5 (ie, the structure of the complex candidate determined by the candidate determination unit 4) by quantum chemical calculation. Decide each.

  The DFT (Density Functional Theory) method and the ab-initio method are known for optimizing the structure of a complex given initial coordinates. For the DFT method, for example, the methods of B3LYP, B3PW91, and MPW1PW91 are used. In the ab-initio method, the Hartree-Hock method, the MP method, or the like is used. As the basis function, for example, 3-21G, 6-31G (d), 6-31 + G (d, f) can be used. For atoms and metals that cannot be handled by these basis functions, LANL2DZ or the like may be used.

  In the case of structure optimization, a vacuum optimization method or a calculation method considering the solvent effect is used. As a calculation method of the solvent effect, a PCM (Polarizable Continuum Model) method, an IEFPCM (Integral Equation Formalism PCM) method, a SCFPCM (Self-Consistent Isodensity Polarized Continuum Model) method, a COMSO (Conductor-like Screening Model) method, or the like is used.

(Spectrum estimation unit 7)
The spectrum estimation unit 7 estimates the intensity for each absorption wavelength of the UV spectrum by TD-DFT calculation for at least a part of the complex candidates determined by the candidate determination unit 4. When performing the TD-DFT calculation, it is preferable to perform the calculation considering the solvent effect described above.

  As a method for performing the TD-DFT calculation, for example, the methods of B3LYP, B3PW91, and MPW1PW91 are used. As the basis function, for example, 3-21G, 6-31G (d), 6-31 + G (d, f), or the like can be used. For atoms and metals that cannot be handled by these basis functions, LANL2DZ or the like may be used.

  However, it is not necessary to use the same method as the method and basis function used for the structure optimization for the TD-DFT calculation. For the solvent effect, PCM method, IEFPCM method, SCFPCM method, COMSO method or the like is used. In particular, 6-31G (d) or MPW1PW91 is preferable as a calculation method, and IEFPCM method is preferable as a solvent effect.

(Absorption curve creation unit 8)
The absorption curve creation unit 8 uses a discrete value (excitation spectrum estimation value) indicating the intensity of the discontinuous UV spectrum wavelength obtained by the spectrum estimation unit 7 using a Gaussian function, a Lorentz function, or a combination of two functions. It is smoothed and converted to a continuous spectral waveform so that it resembles the measured UV-visible absorption spectrum of the transition metal complex.

  The half width at the time of smoothing was measured using a value in the vicinity of 0.2 to 0.5 eV with reference to 0.4 eV described in the Journal of Physical Chemistry A, vol.106, 7399-7406 (2002). What is necessary is just to change a numerical value so that it may become close to the waveform of a spectrum.

  The absorption curve creation unit 8 stores information (estimated UV spectrum data 13b) indicating the created continuous waveform of the UV spectrum in the storage unit 13.

(Comparator 9)
The comparison unit 9 calculates the UV spectrum (estimated UV spectrum) created by the absorption curve creation unit 8 and the actually measured UV spectrum obtained by actually measuring the mixture of the transition metal complex, the organic solvent, and the reactant indicated by the specific information. The estimated UV spectrum most similar to the actually measured UV spectrum is identified. Data indicating the actually measured UV spectrum (actually measured UV spectrum data 13c) is stored in the storage unit 13 in advance.

  More specifically, the comparison unit 9 forms the estimated UV spectrum shape and the measured UV spectrum shape, the wavelength at which the absorption maximum (the peak of the waveform of the UV spectrum) is formed, and the maximum intensity absorption maximum. By comparing the wavelength (λmax), the number of absorption maxima, the intensity ratio of the absorption maxima, and the like, a complex candidate having an estimated UV spectrum having a shape most similar to the shape of the actually measured UV spectrum is selected.

  The comparison unit 9 may use at least one standard for comparing the estimated UV spectrum and the actual UV spectrum, but it is difficult to narrow down the complex candidates to one in the comparison based on only one standard. Therefore, it is preferable to compare a plurality of criteria in combination.

  In addition, the estimated UV spectrum obtained from the TD-DFT calculation may be shifted to the short wavelength side depending on the metal species, so the most similar UV spectrum should be selected in consideration of the effect. Is preferred. The rate of movement to the short wavelength side varies depending on the calculation method. For example, in the case of a Ni complex, an estimated value shifted to the short wavelength side by about 30 to 50 nm as compared with the actually measured UV spectrum is obtained.

(Candidate selection unit 10)
When there are a plurality of complex candidates narrowed down by the comparison unit 9, the candidate selection unit 10 removes complex candidates that are unlikely to exist from these complex candidates. In other words, the candidate selection unit 10 further narrows down the plurality of complex candidates specified by the comparison unit 9. Details of processing in the candidate selection unit 10 will be described later. The candidate selection unit 10 outputs information indicating the narrowed complex candidates to the output unit 12.

  If the number of complex candidates cannot be narrowed down to one, the candidate selection unit 10 may output information indicating the plurality of narrowed complex candidates to the output unit 12.

(Method of determining complex candidates in candidate determination unit 4)
Complex candidates for performing TD-DFT calculation are (1) the reactant itself added to the reaction system, (2) the ligand (second ligand) generated from the reactant, and (3) the coordination from the reactant. Of the compound (reaction product after elimination) generated by desorbing the child and (4) the solvent molecule of the reaction system, and (5) the ligand (first ligand) previously possessed by the transition metal complex All of the complexes bonded or coordinated to the transition metal in a combination of a part or all of

  The candidate determination unit 4 places a transition metal at the center, and forms a complex with all combinations of all ligands, solvent molecules, reactants, and post-elimination reactants that can coordinate to the transition metal.

  And the candidate determination part 4 produces the coupling | bonding table | surface 14 which shows the structure of each complex candidate. As shown in Table 3 to be described later, this binding table 14 indicates the type and number of ligands coordinated to the transition metal and compounds (reactants and post-elimination reactants) that bind to the transition metal. .

(Method for narrowing down complex candidates in the comparison unit 9)
The comparison unit 9 narrows down complex candidates using at least a part of the methods M1 to 4 and M6 shown in Table 1.

  Table 1 shows an example of a method for narrowing down the complex candidates by comparing the actually measured UV spectrum with the estimated UV spectrum from the theoretical calculation. The narrowing-down methods M1, M2, M3, M4, and M6 shown in Table 1 are spectral waveform comparisons and are methods used by the comparison unit 9, but M5 selects complex candidates based on the stability of each complex candidate. This is a method of narrowing down and is a method used by the candidate selection unit 10.

  In the methods of M1 to M4 and M6, in order to enable comparison with the actually measured UV spectrum, it is preferable to compare the absorption maximum of the estimated UV spectrum with a value having a width shifted from the 30 to 50 nm long wavelength side. .

  Further, the wavelength region to be compared depends on the measurement state of the actually measured UV spectrum, but in the wavelength region shorter than 200 nm, a large amount of organic compound is observed, which is not practical. The wavelength region to be compared is preferably between 300 nm and 800 nm in which absorption derived from metal-to-ligand excitation of a normal transition metal complex is observed.

  When the comparison unit 9 cannot identify a single complex candidate by only one of the methods M1 to M4 and M6 shown in Table 1, a plurality of methods may be used in combination. That is, the comparison unit 9 compares the estimated UV spectrum with the actually measured UV spectrum by (M1) the wavelength at which the waveform of the UV spectrum peaks (wavelength at the peak position), and (M2) the maximum of the first derivative curve of the absorption wavelength. Number (ie, the number of peaks in the waveform of the UV spectrum), (M3) difference in wavelength between absorption maxima when there are multiple absorption maxima, (M4) at each absorption maxima when there are multiple absorption maxima This is performed for at least one of the relative ratio of absorption intensity and (M6) comparison of the shape of the entire waveform of the UV spectrum.

  When using a plurality of narrowing-down methods, the order is arbitrary. Among these, the order of M2, M3, and M4 after M1 is preferable. Normally, narrowing down is performed in the order of M1 and M2, but other methods and orders can be specified.

  Although it is desired to finally determine one complex candidate by narrowing down, a plurality of candidates may remain. In that case, since the method M3, M4, and M6 performs quantitative numerical evaluation, it is also possible to rank using the numerical values.

(Details of Method M6)
In the narrowing-down method M6 in Table 1, the overall absorption intensity is corrected so that the characteristic absorption maximum peak of the actually measured UV spectrum matches the absorption maximum peak of the estimated UV spectrum obtained from the TD-DFT calculation. As a characteristic absorption maximum at this time, for example, absorption on the shortest wavelength side can be selected. Further, the wavelength in the range to be compared is limited to, for example, 300 nm to 800 nm.

  Then, the difference between the measured spectrum and the estimated spectrum is quantified by the sum of the squares of the differences in absorption intensity for each unit wavelength. For example, the unit wavelength is 2 nm. The smaller the difference value, the closer it is to the measured spectrum.

  With the narrowing-down method M6, it is possible to narrow down one complex by itself, but since the amount of calculation increases, a combination with other methods is also possible.

(Method for narrowing down complex candidates in the candidate selection unit 10)
The candidate selection unit 10 determines a plurality of complex candidates specified by the comparison unit 9 when there are a plurality of estimated UV spectra specified by the comparison unit 9, that is, when the comparison unit 9 cannot narrow down the complex candidates to one. , Further narrow down the complex candidates by comparing the stability of these complex candidates. A method for narrowing down complex candidates in the candidate selection unit 10 will be described below.

  The comparison of the stability of the complex, which is the narrowing-down method M5 in Table 1, is to compare the degree of stabilization by binding the neutral ligand to the complex by quantifying with energy. A neutral ligand refers to a ligand or solvent having no charge.

  In calculating the stabilization energy of the complex, it is assumed that the complex groups that can be compared have a common complex partial structure. As the common partial structure, for example, a structure in which an anionic ligand R is bonded to a metal, the number of the anionic ligand R is fixed, and the presence or absence of the neutral ligand L and the coordination number are arbitrary ( A classification A) or a classification (classification B) in which the type of neutral ligand is fixed and the number of neutral ligands is arbitrary common partial structure is assumed.

  An anionic ligand is a structure in which a leaving group of a reactant having a leaving group is cleaved, and refers to a ligand provided with an anion and a counter anion of a metal salt. Refers to normal ligands and solvents.

  Table 2 shows examples of classification A and classification B.

  R1 and R2 in Table 2 mean different types of anionic ligands, and L1 and L2 mean different neutral ligands. Regarding classification A in Table 2, a group in which two anionic ligands R1 are coordinated (complex with ID 1 to 7) and a complex group in which R1 and R2 are coordinated one by one (ID is 8) To 12 complexes).

  Moreover, in the category B of Table 2, each group of the category A is further subdivided according to the structure (number and type) of neutral ligands.

  When comparing stability in comparable complex groups with common substructures, the maximum number of ligands per complex for all neutral ligands in the complex group Count by species. The upper limit of the ligand can be specified in the range of 6 or less, but it is desirable to make 6-coordinate the upper limit for the purpose of comprehensively generating possible complex structures.

  For each complex in the group, the difference between the number of each neutral ligand and the maximum number of ligands is taken, and the energy of the neutral ligand of the difference is added to the energy of the original complex. The same energy is calculated for all the complexes, and the complexes are rearranged in order of increasing energy to determine the lowest energy (most stable energy) complex. For the complexes in other groups, the difference from the most stable energy is calculated, and the stability in this complex group is compared by assuming that the larger the value is, the more unstable it is.

  When narrowing down the acceptable complexes to be examined in the comparable complex group having a common partial structure, the difference from the most stable energy can be set to 30 kcal / mol or less.

(Processing flow in the structure estimation apparatus 1)
Next, an example of a processing flow in the structure estimation apparatus 1 will be described with reference to FIG. FIG. 3 is a flowchart illustrating an example of a process flow in the structure estimation apparatus 1.

  First, the acquisition unit 2 acquires specific information for specifying the transition metal complex, the organic solvent, and the target compound from the user via the input unit 11, and the acquired specific information is used as the ligand specification unit 3 and the candidate. It outputs to the determination part 4 (S1) (acquisition process).

  When the specific information is received, the ligand specifying unit 3 refers to the structure data file 13a stored in the storage unit 13 so that the transition metal complex indicated by the specific information has a first ligand, The second ligand generated from the target compound indicated by the specific information and the post-desorption reactant after the second ligand is desorbed from the target compound are specified (S2).

  The ligand specifying unit 3 outputs information indicating the specified first and second ligands and the post-elimination reactant to the candidate determining unit 4.

  The candidate determination unit 4 includes the identification information of the organic solvent molecule indicated by the specific information, the reactant, the first or second ligand specified by the ligand specifying unit 3 or the post-elimination reactant, or a combination thereof. A plurality of transition metal complexes generated by coordinating or binding to the transition metal included in the transition metal complex represented by (1) are determined as complex candidates (S3) (candidate determination step).

  The candidate determination unit 4 assigns an ID to each complex candidate, creates a binding table 14 indicating the structure of each complex candidate, and stores it in the storage unit 13.

  Next, the three-dimensional structure determination unit 5 generates initial three-dimensional coordinates for theoretical calculation from the structure of the complex candidate indicated by the binding table 14, and associates the generated initial three-dimensional coordinates with the ID of the complex candidate. It outputs to the structure optimization part 6 (S4).

  The structure optimization unit 6 uses the theoretical calculation program to optimize the structure of the complex candidate indicated by the initial three-dimensional coordinates generated by the three-dimensional structure determination unit 5 (S5). Examples of the theoretical calculation program include Gaussian (www.gaussian.com) or DMOL3 (www.accelrys.com). As an optimization method, B3LYP or B3PW91 of DFT calculation, MPW1PW91, etc. are mentioned. As the basis function, a highly accurate optimized structure can be obtained by calculating at a level of 6-31G (d) or 6-31 + G (d, f). In addition, the structure optimization usually converges in a shorter time when the calculation is performed in a vacuum, but a calculation method considering the solvent effect can also be used.

  The structure optimization unit 6 outputs information indicating the structure of each optimized complex candidate (optimum structure information) to the spectrum estimation unit 7 in association with the complex candidate ID.

  Upon receipt of the optimum structure information, the spectrum estimation unit 7 estimates the UV spectrum of each complex candidate indicated by the optimum structure information by TD-DFT calculation (S6) (spectrum estimation step). There are Gaussian etc. as a program to calculate.

  In addition to TD-DFT calculation, the CIS method and ZINDO (Zerner's Intermediate Neglect of Differential Overlap) method are known as UV spectrum estimation methods, but TD-DFT calculation is the most accurate when calculating transition metal complexes. Can be estimated well. In the TD-DFT calculation, one point calculation is performed using the optimized structure.

  Furthermore, it is preferable to consider the solvent effect in the estimation of the UV spectrum. Methods for considering the solvent effect include PCM method, CPCM (polarizable conductor calculation model) method, IEFPCM method, Dipole method, IPCM (Isodensity Polarized Continuum Model) method, SCI-PCM (Self-Consistent Isodensity Polarized Continuum Model) PCM method, CPCM method, IEFPCM method, IPCM method and SCI-PCM method are preferable.

  The spectrum estimation unit 7 outputs the estimated discrete value of the estimated UV spectrum of each complex candidate to the absorption curve creation unit 8 in association with the complex candidate ID.

  The absorption curve creation unit 8 smoothes the discrete value indicating the absorption intensity for each UV spectrum wavelength output from the spectrum estimation unit 7 by using a Gaussian function, a Lorentz function, or a combination of two functions, and the transition metal complex. It is converted into a continuous spectrum waveform so as to be similar to the actually measured UV spectrum (S7).

  At that time, the absorption curve creation unit 8 applies the absorption intensity to the peak area. The full width at half maximum may be adjusted appropriately from 0.2 to 0.5 eV. The absorption maximum of the estimated UV spectrum is preferably corrected by several nanometers to several tens of nanometers depending on the type of complex.

  For example, when a TD-DFT calculation is performed using a Ni complex at the B3LYP / 6-31G (d) level and a calculation method that takes into account the solvent effect (IEFPCM method), it is corrected to the longer wavelength side by about 30 to 50 nm. It is preferable to do. In the case of TD-DFT calculation using MPW1PW91 / 6-31G (d) and the same solvent effect, it is preferable to correct the wavelength to the long wavelength side by about 50 to 70 nm.

  The absorption curve creation unit 8 stores information indicating the continuous waveform of the generated estimated UV spectrum (estimated UV spectrum data 13b) in the storage unit 13 in association with the ID of the complex candidate.

  Then, the comparison unit 9 compares the estimated UV spectrum indicated by the estimated UV spectrum data 13b stored in the storage unit 13 with the actually measured UV spectrum indicated by the actually measured UV spectrum data 13c, and approximates the estimated UV spectrum to the actually measured UV spectrum. (S8) (comparison process).

  Specifically, the comparison unit 9 compares the wavelength of the absorption maximum, the number of absorption maximums, and / or the relative intensity of the absorption maximum with the actually measured UV spectrum, and determines the closest estimated UV spectrum complex to the reaction solution. It is presumed to be a complex corresponding to the UV spectrum actually measured.

  When the number of complex candidates is reduced to one by the comparison process in comparison unit 9 (YES in S9), comparison unit 9 outputs information (for example, ID and structural formula) of the reduced complex candidates to one. 12 is output.

  The output unit 12 notifies the user of the estimation result by displaying information on the complex candidate on the display (S11).

  On the other hand, when the number of complex candidates is not narrowed down to one by the comparison process in the comparison unit 9 (NO in S9), the comparison unit 9 outputs the IDs of the plurality of complex candidates narrowed down by itself to the candidate selection unit 10. .

  And the candidate selection part 10 narrows down a complex candidate further by removing the complex candidate with the low possibility of existing from the some complex candidate which has ID output from the comparison part 9 (S10). Specifically, the candidate selection unit 10 refers to the structure data file 13a and the binding table 14, compares the energy of the complex formation reaction energy among the complex candidates, and selects a more stable complex candidate.

  The candidate selection unit 10 outputs the narrowed complex candidate information (for example, ID and structural formula) to the output unit 12.

  The output unit 12 notifies the user of the estimation result by displaying information on the complex candidate on the display (S11).

  The initial three-dimensional coordinates generated by the three-dimensional structure determination unit 5, the optimum structure information generated by the structure optimization unit 6, and the discrete values of the estimated UV spectrum generated by the spectrum estimation unit 7 are temporarily stored in the storage unit 13, respectively. It may be stored.

(Details of processing in candidate determination unit 4)
Next, details of the process (step S3 in FIG. 3) in the candidate determination unit 4 will be described with reference to FIG. FIG. 4 is a flowchart illustrating an example of a process flow in the candidate determination unit 4.

  First, the candidate determination unit 4 acquires information necessary for expressing all the structures of complex candidates that may exist in the reaction system as a binding table by reading the structure data file 13a stored in the storage unit 13. (S31). The join table is usually stored in a structure data file so that information can be easily retrieved. A structure data file stores information about the atoms that make up a compound, such as atomic species, atomic numbers, charges, asymmetry information, and isotope information, as well as information such as bond order between the atoms. Points to the file. An example is the SDFile format proposed by Elsevier MDL (http://www.mdl.com).

  At this time, the candidate determining unit 4 stores information for determining at least one of transition metal complex candidates including Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, or Ag as a structure data file. It can be obtained by reading 13a.

  In addition, the candidate determination unit 4 specifies the maximum number of ligands that can be coordinated to the central metal of the metal complex indicated by the specific information. Specify the valence. The valence is, for example, 0 and 2 for nickel, and 1 and 2 for copper. Moreover, the candidate determination part 4 designates the electric charge of the metal complex which specific information shows. The charge of the metal complex is the charge when the ligand is coordinated to the metal and is neutral if not specified.

  Next, the candidate determination unit 4 selects the transition metal included in the transition metal complex indicated by the first ligand, the second ligand, the post-elimination reactant, and the specific information specified by the ligand specifying unit 3. , Metal M, anionic ligand R, and neutral ligand L (S32). The anion ligand R refers to a ligand to which an anion has been added and a counter anion of a metal salt with respect to two structures obtained by cleaving the leaving group site of a reactant having a leaving group. Leaving groups include halogen, tosylate, mesylate, acetoxy and the like. The neutral ligand refers to a ligand or a solvent added to promote the reaction, or a ligand originally coordinated as a metal raw material.

  Next, the candidate determination unit 4 selects one ligand (for example, anion ligand R1) as an initial value from the anion ligand R and the neutral ligand L classified in step S32 ( S33).

  Next, the candidate determination unit 4 generates a binding table in which the ligand or ligand set selected in step S33 or step S38 described later is coordinated to the metal M (S34).

  The candidate determination unit 4 calculates the charge of the complex from the valence of the metal and the coordination number of the anion ligand based on the binding table, and the valence of the metal and the charge of the complex are calculated. Whether or not the condition specified in step S31 is satisfied is determined. If the condition is satisfied (YES in S35), the process proceeds to step S36. If the condition is not satisfied (NO in S35), the process proceeds to step S37.

  In step S36, the candidate determination unit 4 adds the complex binding table 14 to the structure data file 13a and stores it. In this structure data file 13a, the total binding table of the complex structure obtained by the flow shown in FIG. 4 is stored. FIG. 1 shows only one combination table 14 for convenience.

  In step S37, the candidate determination unit 4 determines the number of ligands that have not been generated so far, and the number of ligands is equal to or less than the number specified in step S31. It is determined whether a combination of L exists.

  If the combination does not exist (NO in S37), candidate determination unit 4 ends the process. If there is a combination (YES in S37), candidate determination unit 4 generates a new combination that has never existed in step 38 (S38). In this case, a combination of at least one ligand selected from an anionic ligand R and a neutral ligand L is sufficient, and the upper limit of the number of ligands must satisfy the conditions set in step S31. I must.

  And the candidate determination part 4 produces | generates the coupling | bonding table | surface of a complex structure based on the combination of the ligand produced | generated by step S38 (S34).

(Example of change)
The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in each embodiment are also included. It is included in the technical scope of the present invention.

  For example, when the comparison unit 9 compares the estimated UV spectrum and the actually measured UV spectrum based on a plurality of different criteria, the narrowing based on each criterion and the narrowing by the candidate selection unit 10 may be combined.

  The structure estimation apparatus 1 further includes a candidate selection unit (candidate selection unit) that removes transition metal complex candidates that are unlikely to exist from the transition metal complex candidates determined by the candidate determination unit 4, and the spectrum estimation unit 7 includes: You may each estimate the UV spectrum of the complex candidate narrowed down by the candidate selection part.

  In other words, the complex selection by the candidate selection unit 10 may be performed on the complex candidates determined by the candidate determination unit 4.

  When the complex candidates are narrowed down by stability at the time of calculating the complex structure, it is preferable not to select only the most stable complex, but also treat a complex that is unstable to some extent as a candidate. For example, complexes that are more unstable than 30 kcal / mol compared to the most stable complexes are excluded from candidate complexes.

  Alternatively, a ligand or solvent adjacent to the metal, or a complex separated by a distance where the reactant is hardly bonded to the metal may be excluded from the candidates. For example, the distance having almost no coupling can be defined as 4 mm or more.

  Furthermore, the heat of reaction in which a ligand, solvent and / or reactant and metal are combined to form a complex is calculated from the energy obtained from the structure optimization. It can also be removed from the complex. In this case, the endothermic reaction heat can be set to 30 kcal / mol or more, for example.

  Moreover, the comparison part 9 may estimate that two types of complexes are mixed in the solution, when the sum of a plurality of estimated UV spectra matches the actually measured UV-visible spectrum.

  There is no suitable complex that reproduces the entire measured UV spectrum in the estimated UV spectrum. However, if some UV spectra can be reproduced, a plurality of complexes may coexist. In that case, when a plurality of estimated spectra are added to form an actually measured UV spectrum, it may be estimated that a plurality of complexes exist in an equilibrium state in the reaction system.

  Alternatively, the user may input specific information for specifying the transition metal complex, the organic solvent, the reactant, the first and second ligands, and the post-elimination reactant through the input unit 11. . In this case, since the acquisition unit 2 acquires the specific information, and the candidate determination unit 4 generates the binding table 14 using the specific information, the ligand specification unit 3 is unnecessary. However, in consideration of the burden on the user, it is preferable to provide the ligand specifying unit 3.

  An embodiment of the present invention will be described below with reference to FIGS.

  UV spectrum was measured for the complex structure in solution when bipyridine (ligand) and benzene bromide (reactant) were added to dicyclooctadienyl nickel (transition metal complex) in tetrahydrofuran solvent. This measured UV spectrum is shown in FIG. The absorption maximum (λmax) was 476 nm.

  On the other hand, specific information for specifying the transition metal complex (dicyclooctadienyl nickel), ligand (bipyridine), reactant (benzene bromide) and solvent (tetrahydrofuran) is input to the structure estimation apparatus 1, and the transition metal The complex structure was estimated.

  First, as a neutral ligand to be coordinated to Ni by treatment in the ligand specific part 3, cyclooctadiene (COD), tetrahydrofuran (THF), bipyridine (Bpy), and bromo anion (Br) as an anionic ligand are used. ), A phenyl anion (Ph) was identified.

  When all combinations obtained from these ligands were generated by the processing in the candidate determination unit 4, 71 types of complexes were obtained. Table 3 shows a list of all 71 complexes. However, this time, the valence of Ni is limited to 0 and 2 which can usually exist relatively stably.

  Three-dimensional initial coordinates were generated for each of the 71 complex structures obtained by the processing in the three-dimensional structure determination unit 5, and the optimized structure was calculated in Gaussian by the processing in the structure optimization unit 6. At this time, B3LYP / 6-31G (d) was used as a calculation method and a basis function.

  Then, TD-DFT calculation is performed by B3LYP / 6-31G (d) using the above optimization structure and the calculation method considering the solvent effect (IEFPCM method) by the processing in the spectrum estimation unit 7. It was.

  And by the process in the absorption curve preparation part 8, the absorption intensity for every absorption wavelength of each complex candidate obtained from TD-DFT calculation was smooth | blunted using the Gaussian function. In this case, 0.4 eV was used as the half width. Table 3 shows the estimated values of the estimated UV spectrum.

  And by the process in the comparison part 9, the complex candidate which shows the estimated UV spectrum nearest to the measurement UV spectrum was searched from 71 complex candidates.

  The measured UV spectrum shown in FIG. 5 has one absorption maximum (λmax) at 476 nm in the range of 300 to 800 nm. In consideration of the fact that the TD-DFT calculation is estimated to be on the short wavelength side of about 30 to 50 nm, as the complexes estimated to have an absorption maximum from 420 to 450 nm, Nos. 8, 10, 16, 29, and 33 Two candidate complexes were found. The estimated spectrum of each complex candidate is shown in FIGS.

  Complexes No. 8 and No. 10 are both diphenyl nickel complexes, and differ only in the coordination number of THF as a solvent. When the stabilization energies of the two complexes were compared by processing in the candidate selection unit 10, No. 10 was more stable at 8.5 kcal / mol, and No. 8 was excluded from the complex candidates.

  Further, for candidate complexes Nos. 10, 16, 29, and 30 narrowed down from the stabilization energy due to the coordination of the solvent by the processing in the comparison unit 9, the first derivative curve of the estimated UV spectrum and the first derivative of the measured UV spectrum The maximum number (peak number) with the curve was compared. Table 4 shows the number of local maximum values of the first derivative curve.

  As shown in Table 4, from the maximum number of the first derivative curve of the UV spectrum, both of the complex No. 16 and the measured value coincide with three, so the complex in the solution has the structure of No. 16. I was able to estimate.

  In this example, the stabilization energy of the complex was used for narrowing down candidates at the time of comparison of estimated UV spectra after TD-DFT calculation, but narrowing down at the time of structure calculation is also possible. Table 5 shows the results of narrowing down the comparison of stability within a complex group in which only an anion ligand of class A is fixed.

  Table 6 shows the results of narrowing down by stability in a complex group in which an anionic ligand of class B is fixed and the type of neutral ligand is fixed. The numbers in Tables 5 and 6 correspond to the complex numbers in Table 3.

  The complexes for which the stability was compared were 18 complexes (No. 6, 9, 14, 20, 24, 28, 34, 42, 48, 53, 54, 56, 62) that could not be optimized by theoretical calculation. , 63, 64, 66, 68, 71). The next column of No. in Tables 5 and 6 is classified into the complex groups for comparison of stability (Class A or Class B) based on the type and number of ligands coordinated to the metals in Table 3. The number of the most stable complex in the complex group is described. In classification, Ph and Br were treated as anionic ligands, and Bpy, COD and THF were treated as neutral ligands for the ligands listed in Table 3.

  The third column in Tables 5 and 6 describes the energy difference from the most stable complex in each group, and the fourth column shows ○ for complexes with energy differences within 30 kcal / mol. X is described in the above complex. Complexes with an energy difference of 30 kcal / mol or more can be excluded by narrowing down. By narrowing down by this stability, the number of complex candidates for performing the TD-DFT calculation can be reduced, and it can be expected to shorten the time required for estimation.

[Embodiment 2]
The following will describe another embodiment of the present invention with reference to FIGS. In addition, about the member similar to Embodiment 1, the same code | symbol is attached | subjected and the description is abbreviate | omitted.

  One of the characteristics of the transition metal complex is that the transition metal d orbital is split by the ligand field and degenerates to take various electronic states. For example, the electron configuration of divalent nickel has 8 electrons in the 3d orbit. In the case of a regular octahedral 6-coordinate, the orbit is split from a low energy orbit into three orbitals of the t2g group (dxy, dxz, dyz) and two orbits of the eg group (dz2, dx2-dy2). The eight electrons enter the t2g group, and the remaining two atoms enter the two orbitals of the eg group separately with parallel spins (Hund's law). The triplet state (high spin state) Take electronic configuration.

  On the other hand, when the ligand enters the plane 4-coordinate even with the same divalent nickel, the d orbitals are split differently, and dxy and dyz are at the same level from the lowest energy, then dx2, dxy, and The highest trajectory is dx2-dy2. In this case, the eight electrons take a pair of electrons from the low energy orbit to the dxy, dyz, dz2, and dxy orbitals and take a singlet state (low spin state) in which no spin exists. NMR measurement is possible only with this low spin state complex.

  The high spin and low spin states are determined by the ligand of the complex, but it is difficult to identify the ligand of the complex by NMR or ESR. In many cases, it is difficult to predict whether or not the position state will be taken.

  The UV spectrum of interest in the present invention is the absorption spectrum of light accompanying the excitation of electrons from HOMO and HOMO to some low energy orbitals to LUMO and LUMO to some high energy orbitals. When the spin state of the complex changes, the orbital levels of HOMO and LUMO occupying the spin also change.

  Therefore, the energy value absorbed and excited by UV changes, and as a result, the absorption maximum and waveform of the observed UV spectrum differ. Since the change of the UV spectrum due to the change of the spin state is faithfully reproduced by the TD-DFT calculation, it is possible to specify the electron spin state in addition to the complex structure from the UV spectrum. That is, it is possible to estimate whether or not there are lone electrons in the orbit without using magnetization measurement (SQUID) or high-frequency ESR.

  The structure estimation apparatus 30 according to the present embodiment is based on such a technical idea. When determining the optimal structure of the complex candidate determined by the candidate determination unit 4, each of the optimal structures having different electronic states is determined. The accuracy of the structure estimation of the transition metal complex is improved by determining the candidate complex and considering its stability.

  FIG. 11 is a schematic diagram illustrating a configuration of the structure estimation apparatus 30. As shown in the figure, unlike the structure estimation apparatus 1, the structure estimation apparatus 30 includes a control unit 31 including a structure optimization unit 32 and a spin multiplicity selection unit (electronic state selection means) 33.

  The structure optimization unit 6 of the structure estimation apparatus 1 described above determines the optimum structure of the structure determined by the three-dimensional structure determination unit 5 by quantum chemistry calculation. At this time, the electronic state of each structure is taken into consideration. There wasn't. For example, the structure optimization unit 6 performs the calculation assuming that the electronic state (spin multiplicity) of each complex candidate is a singlet.

  On the other hand, the structure optimization unit 32 determines the optimum structure in consideration of the electronic state of each complex candidate. Specifically, the structure optimization unit 32 has a plurality of electronic states that can be taken by the transition metal complex candidate as the optimum structure of the transition metal complex candidate indicated by the initial three-dimensional coordinates calculated by the three-dimensional structure determination unit 5. Each of these is determined by quantum chemical calculation. In other words, when the complex candidate has a transition metal that may take a plurality of electronic states, the structure optimization unit 32 determines the optimal structure of the complex candidate for all possible electronic states. decide.

  And the structure optimization part 32 calculates the energy for every complex candidate about all the possible electronic states. The electronic state described here refers to the spin multiplicity. The spin multiplicity may vary depending on the valence of the metal and the ligand, and the number is determined, and is determined by the number of orbitals occupied by lone electrons. For example, when lone electrons occupy one orbit, a compound containing a metal is called a doublet, and a triplet in the case of two orbits.

  For example, in the case of Ni (II), there is a possibility of taking two types of spin multiplicity, singlet and triplet, depending on the ligand, and the singlet is in a low spin state and the triplet is high. Sometimes called a spin state. This singlet complex can be observed by NMR and cannot be observed by ESR, whereas the triplet complex can be observed by magnetization measurement (SQUID) or high-frequency ESR, and cannot be observed by NMR. It becomes.

  In addition, the complex metal information which shows the kind of electronic state which each complex metal can take (which can take 1 to 3 triplets) is stored in the storage unit 13 in advance, and the structure optimization unit 32 What is necessary is just to determine the kind of electronic state of the complex candidate which should be estimated by acquiring complex metal information.

  The spin multiplicity selection unit 33 compares the energy value calculated by the structure optimization unit 32 for each complex candidate, and the spectrum estimation unit 7 calculates the complex candidate in the electronic state having the smallest energy value. Select as. More specifically, the spin multiplicity selection unit 33 calculates the stable spin with the lowest energy among the energy of the electronic state (for example, singlet and triplet energy) calculated by the structure optimization unit 32. A multiplicity is selected, and a complex candidate in an electronic state having the spin multiplicity is selected. Further, for complex candidates having different spin multiplicity close to the most stable energy, for example, within 10 kcal / mol from the most stable energy, all complex candidates may be targets for UV spectrum estimation.

  As described above, the spin multiplicity selection unit 33 selects the electronic state having the lowest energy among the electronic states in the complex candidate of interest estimated by the structure optimization unit 32, and selects the complex candidate having the selected electronic state. Identify. The spin multiplicity selection unit 33 outputs information specifying the selected complex candidate to the spectrum estimation unit 7.

  The spectrum estimation unit 7 estimates the intensity for each absorption wavelength of the UV spectrum of the complex candidate selected by the spin multiplicity selection unit 33 by TD-DFT calculation. The process of the spectrum estimation unit 7 is the same as the process in the structure estimation apparatus 1.

(Processing flow in the structure estimation apparatus 30)
FIG. 12 is a flowchart illustrating an example of a process flow in the structure estimation apparatus 30. The processing from step S41 to S44 shown in the figure is the same as the processing flow from step S1 to S4 shown in FIG.

  In step S45, the structure optimization unit 32 determines the optimum structure indicated by the initial three-dimensional coordinates calculated by the three-dimensional structure determination unit 5 by quantum chemical calculation. At this time, the structure optimization unit 32 adopts the spin multiplicity that can be taken by the target complex candidate, and determines the optimal structure of the complex candidate for each spin multiplicity.

  Specifically, the structure optimization unit 32 refers to the complex metal information stored in the storage unit 13 (information indicating the types of electronic states that can be taken by the complex metal), thereby determining the optimum structure. The type (for example, singlet and triplet) of electronic states that can be taken by the complex metal (transition metal) included in the candidate is determined, and the optimum structure in each determined electronic state is determined for each complex candidate.

  Note that the structure optimization unit 32 assigns a sub-ID to each of the complex candidates having different electronic states when a plurality of electronic states can be taken for the complex candidate of interest. Thereby, a complex candidate that can take a plurality of electronic states has an electronic state (with an ID given to a combination of components (transition metal, organic solvent, ligand, and reactant) constituting the complex candidate. Sub IDs are assigned according to the difference in spin multiplicity). If the sub-IDs are different, they are recognized as different complex candidates.

  Furthermore, the structure optimization unit 32 calculates the energy of the complex candidate in each electronic state (S46). In other words, the structure optimization unit 32 performs energy calculation for all possible spin multiplicity for each complex candidate. For example, when the complex metal included in the target complex candidate can take a singlet and a triplet, the structure optimization unit 32 determines the energy of the complex candidate in the case of singlet and the complex candidate in the case of triplet. To calculate the energy.

  The structure optimization unit 32 associates information indicating the optimal structure (optimum structure information) and energy information indicating the energy of the complex candidate in the optimal structure with the ID and sub ID of the complex candidate, and the spin multiplicity selection unit To 33.

  In step S47, the spin multiplicity selection unit 33 compares the energy indicated by the energy information received from the structure optimization unit 32, and selects a stable spin multiplicity having the lowest energy among a plurality of energies related to the complex candidate of interest. select. In other words, the spin multiplicity selection unit 33 compares the energies of a plurality of complex candidates having the same ID but different sub IDs, and selects the complex candidate having the lowest energy.

  When the energy difference between complex candidates having different sub-IDs among the complex candidates having the same ID is 10 kcal / mol or less, the spin multiplicity selection unit 33 converts both of them into the spectrum estimation unit 7. May be selected as a UV estimation target.

  Then, the spin multiplicity selection unit 33 performs the above-described selection for all complex candidates having different IDs, and associates the optimum structure information of the selected complex candidates with the IDs and sub IDs of the complex candidates, thereby calculating the spectrum estimation unit. 7 is output.

  Upon receipt of the optimal structure information, the spectrum estimation unit 7 estimates the UV spectrum of each complex candidate indicated by the optimal structure information by TD-DFT calculation (S48). The subsequent processing is the same as the processing flow from step S6 to step S11 shown in FIG.

  The complex candidates in the spin multiplicity selection unit 33 may be narrowed down after the comparison of the UV spectra by the comparison unit 9, and the processing timing of the spin multiplicity selection unit 33 is not particularly limited.

(Example of change)
The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in each embodiment are also included. It is included in the technical scope of the present invention.

  Each block of the structure estimation apparatuses 1 and 30 described above, particularly the control units 20 and 31 may be configured by hardware logic, or may be realized by software using a CPU as follows.

  That is, the structure estimation devices 1 and 30 each have a CPU (central processing unit) that executes instructions of a control program that realizes each function, a ROM (read only memory) that stores the program, and a RAM (random access) that expands the program. memory), a storage device (recording medium) such as a memory for storing the program and various data. The object of the present invention is to read the program code (execution format program, intermediate code program, source program) of the control program (structure estimation program) of the structure estimation apparatus 1/30, which is software that implements the functions described above, by a computer This can also be achieved by supplying the recording medium recorded in a possible manner to the structure estimation devices 1 and 30 and reading and executing the program code recorded in the recording medium by the computer (or CPU or MPU).

  Examples of the recording medium include a tape system such as a magnetic tape and a cassette tape, a magnetic disk such as a floppy (registered trademark) disk / hard disk, and an optical disk such as a CD-ROM / MO / MD / DVD / CD-R. Card system such as IC card, IC card (including memory card) / optical card, or semiconductor memory system such as mask ROM / EPROM / EEPROM / flash ROM.

  Moreover, the structure estimation apparatuses 1 and 30 may be configured to be connectable to a communication network, and the program code may be supplied via the communication network. The communication network is not particularly limited. For example, the Internet, intranet, extranet, LAN, ISDN, VAN, CATV communication network, virtual private network, telephone line network, mobile communication network, satellite communication. A net or the like is available. Also, the transmission medium constituting the communication network is not particularly limited. For example, even in the case of wired such as IEEE 1394, USB, power line carrier, cable TV line, telephone line, ADSL line, etc., infrared rays such as IrDA and remote control, Bluetooth ( (Registered trademark), 802.11 wireless, HDR, mobile phone network, satellite line, terrestrial digital network, and the like can also be used. The present invention can also be realized in the form of a computer data signal embedded in a carrier wave in which the program code is embodied by electronic transmission.

Another embodiment of the present invention will be described below with reference to FIGS. Here, a case where dibromonickel (NiBr ₂ ) and bipyridine (Bpy) are dissolved in tetrahydrofuran (THF) will be described. FIG. 13 is a diagram showing an actual measurement UV spectrum of a solution in which dibromonickel and bipyridine are dissolved in tetrahydrofuran.

  As shown in FIG. 13, the UV spectrum of a solution of dibromonickel and bipyridine dissolved in tetrahydrofuran has an absorption maximum (λmax) of 702 nm, and absorption was observed at 350 nm and 430 nm.

  The combination of dibromonickel (transition metal), bipyridine (ligand) and tetrahydrofuran (solvent) does not produce reactants, and it is known that in solution the ligand and solvent ligand to the transition metal. .

  Therefore, specific information for specifying the transition metal complex (dibromonickel), the ligand (bipyridine), and the solvent (tetrahydrofuran) was input to the structure estimation apparatus 30 to estimate the transition metal complex structure.

  First, tetrahydrofuran (THF) and bipyridine (Bpy) were specified as neutral ligands to be coordinated to dibromonickel by the treatment in the ligand specifying unit 3.

  When all combinations obtained from the neutral ligand and dibromonickel were generated by the processing in the candidate determination unit 4, nine types of complex candidates were obtained. Table 7 shows a list of all nine types of complex candidates. In addition, since the bromo anion of the anion ligand does not react, only the complex bonded to Ni needs to be considered.

  Three-dimensional initial coordinates are generated for each of the nine types of complex candidates obtained by the processing in the three-dimensional structure determination unit 5, and the optimized structure is calculated in Gaussian by the processing in the structure optimization unit 32. At this time, B3LYP / 6-31G (d) was used as a calculation method and a basis function.

  At this time, the structure optimization part 32 determined the optimal structure in the case of a singlet and a triplet about each of nine types of complex candidates. Since Ni is divalent, singlet and triplet are considered for the spin multiplicity. This information is stored in advance in the storage unit 13 and is referred to by the structure optimization unit 32.

  Furthermore, the energy in the case of singlet and the energy in the case of triplet were calculated for each complex candidate by the structure optimization unit 32.

  Then, the energy calculated by the structure optimization unit 32 is compared for each complex candidate by the spin multiplicity selection unit 33, and a stable spin multiplicity having the lowest energy is selected from among a plurality of energies related to the complex candidate to be noticed. It was done.

  For all nine types shown in Table 7 (Nos. 1 to 9), the energy in the triplet is smaller than the energy in the singlet, and the energy difference from each singlet is Since it is 10 kcal / mol or more, one having a triplet was selected for each complex candidate.

  The optimal structure information of the complex candidate selected by the spin multiplicity selection unit 33 is output to the spectrum estimation unit 7, and the calculation method (IEFPCM) considering the solvent effect using the optimized structure by the processing in the spectrum estimation unit 7. TD-DFT calculation was performed using B3LYP / 6-31G (d).

  And by the process in the absorption curve preparation part 8, the absorption intensity for every absorption wavelength of each complex candidate obtained from TD-DFT calculation was smooth | blunted using the Gaussian function. Table 7 shows the estimated value (λmax) of the estimated UV spectrum. For reference, Table 7 shows the result of estimating the UV spectrum (λmax) by TD-DFT calculation for the unstable spin multiplicity (singlet) electronic state.

  And by the process in the comparison part 9, the complex candidate which shows the estimated UV spectrum nearest to the measurement UV spectrum was searched from nine types of complex candidates. As a result, regarding the number and wavelength of the absorption maximum, the complex candidate closest to the actually measured UV spectrum was No. 2. The estimated UV spectrum of the candidate No. 2 is as shown in FIG.

  From the above estimation results, it was speculated that the complex structure of dibromonickel and bipyridine in tetrahydrofuran was No. 2, and the spin multiplicity was triplet. This suggests that this complex cannot be identified by NMR.

  The following will describe still another embodiment of the present invention. Here, the process result in the structure estimation apparatus 30 at the time of melt | dissolving the substance similar to Example 1 in the same organic solvent is shown. Note that the description of the same processing as in the first embodiment is omitted, and the description is started from the processing in the three-dimensional structure determination unit 5.

  As a result of the processing in the three-dimensional structure determination unit 5, three-dimensional initial coordinates were generated for the 71 types of complex structures (shown in Table 8) obtained.

  Then, the optimized structure is calculated by Gaussian by the processing in the structure optimization unit 32. At this time, the structure optimization part 32 determined the optimal structure in the case of a singlet and a triplet about each of 71 types of complex candidates. In the case of Ni valence of 0 and divalent, the spin multiplicity can take singlet and triplet, so the structure of each complex was optimized with two types of spin multiplicity. Furthermore, the energy in the case of singlet and the energy in the case of triplet were calculated for each complex candidate by the structure optimization unit 32.

  Then, the energy calculated by the structure optimization unit 32 is compared for each complex candidate by the spin multiplicity selection unit 33, and a complex candidate with a lower spin multiplicity among a plurality of energies related to the complex candidate to be noticed. Was selected.

  As shown in Table 8, out of 71 types (No. 1 to 71), except for those that could not be determined because the structure was difficult to converge, either singlet or triplet was It was determined whether the energy was small.

  The optimal structure information of the complex candidate selected by the spin multiplicity selection unit 33 is output to the spectrum estimation unit 7, and the calculation method (IEFPCM) considering the solvent effect using the optimized structure by the processing in the spectrum estimation unit 7. TD-DFT calculation was performed using B3LYP / 6-31G (d).

  And by the process in the absorption curve preparation part 8, the absorption intensity for every absorption wavelength of each complex candidate obtained from TD-DFT calculation was smooth | blunted using the Gaussian function. In this case, 0.4 eV was used as the half width. Table 8 shows the estimated value (λmax) of the estimated UV spectrum.

  And by the process in the comparison part 9, the complex candidate which shows the estimated UV spectrum nearest to the measurement UV spectrum was searched from 71 complex candidates.

  The measured UV spectrum shown in FIG. 5 has one absorption maximum (λmax) at 476 nm in the range of 300 to 800 nm. In consideration of the fact that the TD-DFT calculation is estimated to be about 30 to 50 nm on the short wavelength side, the complexes estimated as having an absorption maximum from 420 to 450 nm are 5 of Nos. 8, 9, 10, 16, and 31. Two candidate complexes were found. The estimated spectra of each complex candidate are shown in FIG. 6 to FIG. 8, FIG. 15 and FIG. FIG. 15 is a diagram showing an estimated UV spectrum of Complex No. 31. FIG. 16 is a diagram showing an estimated UV spectrum of Complex No. 9.

  Complexes No. 8, No. 9 and No. 10 are all diphenyl nickel complexes, and differ only in the coordination number of the solvent THF. When the stabilization energies of the three complexes were compared by the processing in the candidate selection unit 10, No. 10 was more stable at 4.5 kcal / mol, and No. 8 and No. 9 were excluded from the complex candidates.

  Further, for candidate complexes Nos. 10, 16 and 31 narrowed down from the stabilization energy due to the coordination of the solvent by the processing in the comparison unit 9, the first derivative curve of the estimated UV spectrum and the first derivative curve of the measured UV spectrum The maximum number (peak number) of was compared. Table 9 shows the number of local maximum values of the primary differential curve.

  As shown in Table 9, from the maximum number of the first derivative curve of the UV spectrum, both of the complex No. 16 and the measured value coincide with three, so the complex in the solution has the structure of No. 16. I was able to estimate.

  As shown in Examples 2 and 3, the structure estimation apparatus 30 can estimate the complex structure with higher accuracy than the structure estimation apparatus 1 by considering the electronic state of the complex candidate. There is a high possibility that a complex structure that cannot be estimated can be accurately estimated.

(Another expression of the present invention)
The present invention can also be expressed as follows.

  That is, the structure estimation method of a transition metal complex in an organic solvent according to the present invention includes a first step of inputting a combination of a solvent, a transition metal, a ligand and a reactant, and a combination input in the first step. The second step of generating the optimum structure of the transition metal complex in the organic solvent by quantum chemical calculation, and each optimum structure by the time-dependent density functional method based on the optimum structure generated in the second step. A third step of estimating the ultraviolet-visible absorption spectrum of the sample, and a fourth step of comparing the ultraviolet-visible absorption spectrum estimated in the third step with the ultraviolet-visible absorption spectrum actually measured in the reaction. It is a feature.

  In the structure estimation method, the transition metal is preferably at least one selected from Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, and Ag.

  In the structure estimation method, the transition metal complex is preferably Ni or Cu.

  The program for estimating the structure of a transition metal complex in an organic solution according to the present invention is a means for generating an optimum structure of a transition metal complex in an organic solvent by quantum chemical calculation for a combination of a solvent, a transition metal, a ligand, and a reactant. Means for estimating the UV-visible absorption spectrum of each optimum structure by a time-dependent density functional method based on the generated optimum structure, and the estimated UV-visible absorption spectrum and the UV-visible absorption spectrum actually measured by the reaction. And a means for comparison.

  In the structure estimation program, the transition metal is preferably at least one selected from Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, and Ag.

  In the structure estimation program, the transition metal complex is preferably Ni or Cu.

  Since the structure of the unstable transition metal complex existing in the organic synthesis reaction system can be estimated by using the structure estimation apparatus of the present invention, it is an efficient catalyst in the industry that produces organic compounds by the organic synthesis reaction. Can encourage the development of

It is the schematic which shows the structure of the structure estimation apparatus which concerns on embodiment of this invention. It is a figure which shows the energy diagram of a catalytic reaction. It is a flowchart which shows an example of the flow of a process in the said structure estimation apparatus. It is a flowchart which shows an example of the flow of a process in a candidate determination part. It is a figure which shows an example of measured UV spectrum. Complex No. which is one of the complex candidates determined by the candidate determination unit. FIG. 8 is a diagram showing an estimated UV spectrum of 8; Complex No. which is one of the complex candidates determined by the candidate determination unit. It is a figure which shows 10 estimated UV spectra. Complex No. which is one of the complex candidates determined by the candidate determination unit. It is a figure which shows 16 estimated UV spectra. Complex No. which is one of the complex candidates determined by the candidate determination unit. It is a figure which shows 29 estimation UV spectrum. Complex No. which is one of the complex candidates determined by the candidate determination unit. It is a figure which shows 33 estimation UV spectrum. It is the schematic which shows the structure of the structure estimation apparatus which concerns on another embodiment of this invention. It is a flowchart which shows an example of the flow of a process in the said structure estimation apparatus. It is a figure which shows the measurement UV spectrum of the solution which melt | dissolved dibromo nickel and bipyridine in tetrahydrofuran. It is a figure which shows the estimated UV spectrum of the complex No. 2 which is one of the complex candidates. It is a figure which shows the estimated UV spectrum of the complex No.31 which is one of the complex candidates. It is a figure which shows the estimated UV spectrum of the complex No.9 which is one of the complex candidates.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Structure estimation apparatus 2 Acquisition part (acquisition means)
3 Ligand identification part (Ligand identification means)
4 Candidate decision part (candidate decision means)
7 Spectrum estimation part (spectrum estimation means)
9 Comparison part (comparison means)
10 Candidate selection unit (candidate selection means)
DESCRIPTION OF SYMBOLS 11 Input part 12 Output part 13 Memory | storage part 13a Structure data file 13b Estimation UV spectrum data 13c Actual measurement UV spectrum data 30 Structure estimation apparatus 32 Structure optimization part (structure optimization means)
33 Spin multiplicity selection unit (electronic state selection means)

Claims (12)

A structure estimation apparatus for estimating the structure of a transition metal complex that catalyzes a chemical reaction in a reaction system including an organic solvent,
An acquisition means for acquiring specific information for specifying each of the transition metal complex, the organic solvent, and at least one target compound to be a catalyst of the transition metal complex,
Candidate determination means for determining a plurality of transition metal complexes that may be generated by mixing the transition metal complex, the organic solvent, and the target compound indicated by the specific information acquired by the acquisition means as transition metal complex candidates;
Spectrum estimation means for estimating an ultraviolet-visible absorption spectrum of at least a part of the transition metal complex candidate determined by the candidate determination means;
The estimated UV-visible absorption spectrum estimated by the spectrum estimation means and the measured UV-visible absorption spectrum obtained by actually measuring the UV-visible absorption spectrum of the mixture of the transition metal complex, the organic solvent and the target compound indicated by the specific information. A structure estimation device comprising comparison means for comparing and specifying an estimated ultraviolet-visible absorption spectrum similar to the actually measured ultraviolet-visible absorption spectrum. The 1st ligand which the transition metal complex which the specific information which the said acquisition means shows has has, the 2nd ligand which may arise from the target compound which the above-mentioned specific information shows, and the 2nd ligand concerned Further comprising a ligand identifying means for identifying the compound after desorption after desorption from the target compound,
The candidate determination means includes at least one kind selected from the group consisting of an organic solvent indicated by the identification information, a target compound, the first and second ligands identified by the ligand identification means, and a compound after elimination. 2. The structure according to claim 1, wherein a plurality of transition metal complexes generated by coordination or binding of a substance to a transition metal contained in the transition metal complex indicated by the specific information are determined as transition metal complex candidates. Estimating device.   When there are multiple estimated UV-visible absorption spectra identified by the above comparison means, remove chemically unstable transition metal complex candidates from the multiple transition metal complex candidates from which the estimated UV-visible absorption spectra are estimated The structure estimation apparatus according to claim 1, further comprising candidate selection means for performing the selection. Candidate selection means for removing chemically unstable transition metal complex candidates from the transition metal complex candidates determined by the candidate determination means,
The structure estimation apparatus according to claim 1, wherein the spectrum estimation unit estimates an ultraviolet-visible absorption spectrum of transition metal complex candidates narrowed down by the candidate selection unit. A structure optimization means for determining a chemically stable structure of the transition metal complex candidate determined by the candidate determination means by quantum chemical calculation;
The structure estimation apparatus according to claim 1, wherein the spectrum estimation unit estimates an ultraviolet-visible absorption spectrum of the structure determined by the structure optimization unit.   The structure estimation apparatus according to claim 1, wherein the spectrum estimation unit calculates an estimated ultraviolet-visible absorption spectrum by a time-dependent density functional method.   The candidate determining means acquires information for determining at least one of transition metal complex candidates including Ni, Cu, Fe, Cr, Co, V, Mn, Mo, Ru, or Ag. The structure estimation apparatus according to any one of claims 1 to 6.   A structure estimation program for operating the structure estimation apparatus according to claim 1, wherein the computer functions as each of the means.   A computer-readable recording medium on which the structure estimation program according to claim 8 is recorded. A structure estimation method in a structure estimation apparatus for estimating a structure of a transition metal complex that catalyzes a chemical reaction in a reaction system including an organic solvent,
An acquisition step of acquiring specific information for identifying each of the transition metal complex, the organic solvent, and at least one target compound that is a catalyst target of the transition metal complex;
A candidate determination step of determining a plurality of transition metal complexes that may be generated by mixing the transition metal complex, the organic solvent, and the target compound indicated by the specific information acquired in the acquisition step as transition metal complex candidates;
A spectrum estimation step of estimating an ultraviolet-visible absorption spectrum of at least a part of the transition metal complex candidate determined in the candidate determination step;
The estimated ultraviolet-visible absorption spectrum estimated in the spectrum estimating step, and the measured ultraviolet-visible absorption spectrum obtained by actually measuring the ultraviolet-visible absorption spectrum of the mixture of the transition metal complex, the organic solvent and the target compound indicated by the specific information, And a comparison step of specifying an estimated ultraviolet-visible absorption spectrum similar to the actually measured ultraviolet-visible absorption spectrum.   6. The structure estimation apparatus according to claim 5, wherein the structure optimization means determines a chemically most stable structure for each of a plurality of electronic states that can be taken by the transition metal complex candidate. The structure optimization means calculates the energy value of the transition metal complex candidate for each of the electronic states,
The energy value calculated by the structure optimization means is compared for each transition metal complex candidate, and the transition metal complex candidate in the electronic state having the smallest energy value is used as an estimation target of the UV-visible absorption spectrum by the spectrum estimation means. The structure estimation apparatus according to claim 11, further comprising electronic state selection means for selecting.

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