WO2006057785A2 - Pentacyanochromate(ii) and nonacyanodichromate(ii) compositions and uses thereof - Google Patents

Pentacyanochromate(ii) and nonacyanodichromate(ii) compositions and uses thereof Download PDF

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WO2006057785A2
WO2006057785A2 PCT/US2005/039771 US2005039771W WO2006057785A2 WO 2006057785 A2 WO2006057785 A2 WO 2006057785A2 US 2005039771 W US2005039771 W US 2005039771W WO 2006057785 A2 WO2006057785 A2 WO 2006057785A2
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magnetic material
pentacyanochromate
mecn
solution
dissolved
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WO2006057785A3 (en
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Kendric J. Nelson
Joel S. Miller
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University Of Utah Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/11—Complex cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
    • C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/42—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of organic or organo-metallic materials, e.g. graphene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/42—Magnetic properties

Definitions

  • the present invention is in the field of chemistry and relates to novel pentacyanochromate(ll) and nonacyanodichromate(ll) compounds including their solvated and polymeric forms; more particularly, the present invention relates to compounds with the formulas [NEt 4 ] 3 [Cr"(CN) 5 ] (1) and (2).
  • the present invention further relates to methods of making and using coordinatively unsaturated cyanochromate(ll) compounds.
  • Chromium(ll) is an extremely labile transition metal which, in solution, exchanges ligands at the rate of diffusion (i.e., as fast as a free ligand moves to the metal center and binds, a bound ligand dissociates and moves away). Labile and coordinatively unsaturated complexes can be useful as catalysts because substrates are able to enter the metal coordination sphere with relatively little physical (steric) or electronic repulsion. Once a substrate is bound to the metal, it can be chemically transformed by a ligand that is bound on the same metal or by a substrate in solution. Following the chemical transformation of the substrate, the substrate dissociates from the metal and the catalyst is free to transform another incoming substrate. Many polymerization catalysts, for example, operate by this type of mechanism. Chromium(ll) is also strongly reducing; it easily loses electrons to form Cr 3+ ,
  • Reducing agents such as Cr(II) are useful in many organic reactions (e.g., reductions of aldehydes, alcohols, alkynes and alkenes).
  • a third characteristic of interest with regard to chromium(ll) is that, in the novel compounds described herein, Cr 2+ contains 4 unpaired electrons. Unpaired electrons are responsible for magnetic phenomena, so the compounds described herein may be used as building blocks for magnetic materials.
  • the present invention is in the field of chemistry and relates to novel pentacyanochromate(ll) and nonacyanodichromate(ll) compounds including their solvated and polymeric forms; more particularly, the present invention relates to compounds with the formulas [NEt 4 ] 3 [Cr"(CN) 5 ] (1) and [NEt 4 ] 5 [Cr" 2 (CN) 9 ] (2).
  • the present invention further relates to methods of making and using coordinatively unsaturated cyanochromate(ll) compounds.
  • the present invention relates to methods of using compounds of formula (1) and/or (2) to promote or catalyze organic reactions, including reductions and polymerizations, or as building blocks for magnetic materials which may be useful for a variety of applications (e.g., data storage, sensors, automobile engines, medical imaging, acoustics).
  • applications e.g., data storage, sensors, automobile engines, medical imaging, acoustics.
  • Another aspect of the present invention provides methods of preparing compounds of formula (1) and (2). It will be understood by one skilled in the art that several Cr" sources and counterions may be used without departing from the spirit and scope of the invention.
  • Another aspect of the present invention relates to the use of (1) and/or (2) as a building block for molecule-based magnetic materials with the general formulas M 111 ICr 11 CCN) 5 ] (3), M 11 M 111 ICr 1 ⁇ (CN) 9 ] (4), M" 3 [Cr"(CN) 5 ] 2 (5) and the like, where ancillary cations, anions and/or solvation molecules may be present.
  • Molecule-based magnetic materials as opposed to metallic and/or ceramic magnets or alloys, are synthesized by conventional inorganic and organic methodologies at relatively low temperatures.
  • the synthetic chemist has the ability to "tune” and combine the properties (e.g., magnetic, optical, polymeric, conducting) of the material by controlling the size, conjugation and number of ligands, as well as which metal (M) to use.
  • Figure 1 illustrates the crystal structure of the two unique cyanochromate anions.
  • (1) and/or (2) may be used as a reducing agent.
  • exemplary moieties that may be reduced by (1) and/or (2) include alkynes, alkenes, aldehydes, alcohols and other chemical entities with standard reduction potentials greater than about -0.42 V relative to the standard hydrogen electrode (SHE).
  • SHE standard hydrogen electrode
  • (1) and/or (2) may be used as a catalyst.
  • the cobalt(ll) analog [Co"(CN) 5 ] 3 ⁇
  • the unsaturated nature of the cyanochromate complexes provides the opportunity for substrates to bind to the chromium center with relatively little steric or electronic repulsion from neighboring ligands.
  • the substrate Upon binding to the metal, the substrate may become activated toward other nearby substrates. Following the reaction with a nearby substrate, the metal may release the bound substrate into solution and become available for further substrate transformations.
  • (1) and/or (2) may catalyze a polymerization reaction where monomers react to form polymer chains.
  • the catalysts may operate under homogeneous or heterogeneous conditions, and it may be desirable or necessary to add co-catalysts or initiators, as described in the art.
  • (1) and/or (2) may be used as a building block in the synthesis of molecule-based magnetic materials with the general formulas M'"[Cr"(CN) 5 ] (3), M 11 M 111 CCr 1 ⁇ (CN) 9 ] (4), M" 3 [Cr"(CN) 5 ] 2 (5) and the like, where ancillary cations, anions and/or salvation molecules may be present.
  • Such materials may be synthesized, for example, by the methods shown in Schemes 1-3 below:
  • [NEt 4 ] 3 [Cr"(CN) 5 ] (1) is used as a building block for a magnetic material with the formula M"'[Cr"(CN) 5 ] (3), which may be accomplished for example by dissolving one equivalent of a M 1 " source, such as and adding it dropwise to one equivalent of [NEt 4 ] 3 [Cr"(CN)5] (1) dissolved in the same solvent to form the polymeric magnetic material M lM [Cr"(CN) 5 ]
  • (2) is used as a building block for a magnetic material with the formula M 11 M 111 ICr 1 ⁇ (CN) 9 ] (4), which may be accomplished for example by dissolving one equivalent of a M 1 " source, such as M lll (MeCN) 6 (BF 4 ) 2 , and adding it dropwise to one equivalent of (2) dissolved in the same solvent to form the polymeric magnetic material
  • [NEt 4 ] 3 [Cr"(CN) 5 ] (1) is used as a building block for a magnetic material with the formula M" 3 [Cr n (CN)5]2 (5), which may be accomplished for example by dissolving one equivalent of a M 1 " source, such as
  • chromium(ll) Cr(II)
  • Cr 2+ Cr 2+
  • Cr chromium
  • ligand shall refer to an organic species that binds to one or more metal cations.
  • a ligand may form a bridge between two or more metal cations.
  • Ligands in general, are negatively charged species (e.g., CN ' ) or uncharged species presenting a lone electron pair that interacts electrostatically with a metal cation (e.g., MeCN).
  • the term "coordinatively unsaturated” shall be used to refer to a metal complex that contains fewer than the theoretically allowed number of ligands, as determined by the metal orbitals available for bonding. While 7 ligands may bond to Cr(II), typically, a transition metal is considered saturated if it is surrounded by 6 ligands; thus, a transition metal complex containing 5 or fewer ligands may be considered coordinatively unsaturated.
  • counterion shall refer to an organic cation that does not tightly bind a corresponding anion, in this case the cyanochromates. Counterions are typically large so that charge may be widely distributed. Exemplary counterions include tetramethylammonium (NMe 4 + ), tetraethylammonium (NEt 4 + ), tetrapropylammonium (NPr 4 + ), f-butylammonium (TBA), tetraphenylphosphonium (PPh 4 + ), tetraphenylarsonium (AsPh 4 + ), methyltriphenylphosphonium (Ph 3 MeP + ), methyltriphenylarsonium (Ph 3 MeAs + ), methyl pyridinium (Me (S-X) C 5 H x NH + ) and the like.
  • NMe 4 + tetramethylammonium
  • NEt 4 + tetraethylammonium
  • Cr source shall refer to a reactant containing at least one Cr atom in a 2+ or (II) oxidation state. Chromium(ll) from the "Cr” source” will be incorporated into the final product.
  • a Cr” source typically contains large, negatively charged anions or ligands (e.g., BF 4 " , OAc ' , BARF “ , CIO 4 “ ) that may be easily replaced by cyanide (CN “ ).
  • a metal or “an anion” refers to one or more of those compounds, or at least one compound.
  • a metal or “an anion” refers to one or more of those compounds, or at least one compound.
  • the terms “a” or “an”, “one or more” and “at least one” can be used interchangeably herein.
  • the terms “comprising”, “including”, and “having” can be used interchangeably.
  • a compound “selected from the group consisting of refers to one or more of the compounds in the list that follows, including mixtures (i.e., combinations) of two or more of the compounds.
  • NEt 4 CN was prepared by reacting NaCN and NEt 4 CI in
  • Example 2 Synthesis and characterization of [NEU] 8 [Cr"(CN) 5 ][Cr" 2 (CN) 9 ]'2MeCN, containing [NEUk[Cr 11 CCN) 5 ] and [NEU] 5 [Cr 1 ⁇ (CN) 9 ] Cr" 2 (OAc) 4 (55.94 mg, 0.1644 mmol, 1.00 eq.) was dissolved in 40 mL of
  • a solution of (1) and/or (2) may be added by separatory funnel, cannula, syringe or other known means.
  • the reaction vessel may be cooled or heated as necessary and the progress of the reaction may be monitored by thin layer chromatography (TLC), for example.
  • TLC thin layer chromatography
  • the product may be isolated from side- products and/or remaining starting material by silica gel chromatography, crystallization or other available means.
  • Example 4 Use of (1) and/or (2) as a catalyst
  • a catalytic amount of (1) and/or (2) dissolved in a minimal amount of solvent is added.
  • a co-catalyst and/or initiator are optionally added.
  • (1) and/or (2) catalyze the conversion of cyclopropene to polypropylene.
  • Example 5 Use of (1) as a building block for a magnetic material with the formula M 111 ICr 11 CCN) 5 ] (3)
  • M 1 " source such as M'"(MeCN) 6 (BF 4 ) 3
  • a suitable solvent e.g., MeCN, THF, CH 2 CI 2
  • the solution is stirred for 10-30 minutes and then filtered.
  • one equivalent of [NEt 4 ] 3 [Cr"(CN) 5 ] (1) is dissolved, preferably using the same solvent as that used for the M 1 " source.
  • the solution containing M'"(MeCN)6(BF 4 ) 3 is added dropwise to the pentacyanochromate solution with constant stirring.
  • the polymeric magnetic material formed, M'"[Cr"(CN)5] will precipitate and may be collected by filtration and washed to remove impurities.
  • Example 6 Use of (2) as a building block for a magnetic material including M 11 M 111 ICr 1 ⁇ (CN) 9 ] (4)
  • a M 1 " source, such as M"'(MeCN)6(BF 4 ) 3 , and a M 11 source, such as M"(MeCN) 6 (BF 4 ) 2 , may be dissolved in a single flask using a suitable solvent (e.g.,
  • Example 7 Use of (1) as a building block for a magnetic material with the formula M" 3 [Cr"(CN) 5 ] 2 (5)
  • M"(MeCN) 6 BF 4
  • a suitable solvent e.g., MeCN, THF, CH 2 CI 2
  • the solution is stirred for 10-30 minutes and then filtered.
  • two equivalents of [NEt 4 ] 3 [Cr"(CN) 5 ] (1) are dissolved, preferably using the same solvent as that used for the M source.
  • the M n solution is added dropwise to the pentacyanochromate solution with constant stirring.
  • the polymeric magnetic material formed, M" 3 [Cr"(CN) 5 ] 2 will precipitate and may be collected by filtration and washed to remove impurities.

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Abstract

The present invention relates to novel pentacyanochromate(II) and nonacyanodichromate(II) compounds including their solvated and polymeric forms. Particularly, compounds with the formulas [NEt4]3[CrII(CN)5] (1) and [NEt4]5[CrII2(CN)9] (2) and methods of making and using coordinatively unsaturated cyanochromate(II) compounds, for example, as catalysts, reducing agents or building blocks for magnetic materials are disclosed.

Description

PENTACYANOCHROMATE(II) AND NONACYANODICHROMATE(II) COMPOSITIONS AND USES THEREOF
STATEMENT OF FEDERAL FUNDING This invention was made with government support under Grant Nos. DE FG
03-93ER45504 and 35165-AC5 awarded by the US Department of Energy and the American Chemical Society Petroleum Research Fund, respectively. The government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention is in the field of chemistry and relates to novel pentacyanochromate(ll) and nonacyanodichromate(ll) compounds including their solvated and polymeric forms; more particularly, the present invention relates to compounds with the formulas [NEt4]3[Cr"(CN)5] (1) and
Figure imgf000002_0001
(2). The present invention further relates to methods of making and using coordinatively unsaturated cyanochromate(ll) compounds.
BACKGROUND OF THE INVENTION
Chromium(ll) is an extremely labile transition metal which, in solution, exchanges ligands at the rate of diffusion (i.e., as fast as a free ligand moves to the metal center and binds, a bound ligand dissociates and moves away). Labile and coordinatively unsaturated complexes can be useful as catalysts because substrates are able to enter the metal coordination sphere with relatively little physical (steric) or electronic repulsion. Once a substrate is bound to the metal, it can be chemically transformed by a ligand that is bound on the same metal or by a substrate in solution. Following the chemical transformation of the substrate, the substrate dissociates from the metal and the catalyst is free to transform another incoming substrate. Many polymerization catalysts, for example, operate by this type of mechanism. Chromium(ll) is also strongly reducing; it easily loses electrons to form Cr3+,
Cr4+, Cr5+ and Cr6+. Reducing agents, such as Cr(II), are useful in many organic reactions (e.g., reductions of aldehydes, alcohols, alkynes and alkenes).
A third characteristic of interest with regard to chromium(ll) is that, in the novel compounds described herein, Cr2+ contains 4 unpaired electrons. Unpaired electrons are responsible for magnetic phenomena, so the compounds described herein may be used as building blocks for magnetic materials.
SUMMARY OF THE INVENTION The present invention is in the field of chemistry and relates to novel pentacyanochromate(ll) and nonacyanodichromate(ll) compounds including their solvated and polymeric forms; more particularly, the present invention relates to compounds with the formulas [NEt4]3[Cr"(CN)5] (1) and [NEt4]5[Cr"2(CN)9] (2). The present invention further relates to methods of making and using coordinatively unsaturated cyanochromate(ll) compounds.
The present invention relates to methods of using compounds of formula (1) and/or (2) to promote or catalyze organic reactions, including reductions and polymerizations, or as building blocks for magnetic materials which may be useful for a variety of applications (e.g., data storage, sensors, automobile engines, medical imaging, acoustics).
Another aspect of the present invention provides methods of preparing compounds of formula (1) and (2). It will be understood by one skilled in the art that several Cr" sources and counterions may be used without departing from the spirit and scope of the invention. Another aspect of the present invention relates to the use of (1) and/or (2) as a building block for molecule-based magnetic materials with the general formulas M111ICr11CCN)5] (3), M11M111ICr1^(CN)9] (4), M"3[Cr"(CN)5]2 (5) and the like, where ancillary cations, anions and/or solvation molecules may be present. Molecule-based magnetic materials, as opposed to metallic and/or ceramic magnets or alloys, are synthesized by conventional inorganic and organic methodologies at relatively low temperatures. Thus, the synthetic chemist has the ability to "tune" and combine the properties (e.g., magnetic, optical, polymeric, conducting) of the material by controlling the size, conjugation and number of ligands, as well as which metal (M) to use.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention described in this specification will be better understood when taken in conjunction with the drawings wherein: Figure 1 illustrates the crystal structure of the two unique cyanochromate anions.
DETAILED DESCRIPTION OF THE INVENTION It is to be understood that this invention is not limited to methodology, protocol or reagents described herein. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments and should not be construed as limiting.
In one embodiment of the present invention, (1) and/or (2) may be used as a reducing agent. Exemplary moieties that may be reduced by (1) and/or (2) include alkynes, alkenes, aldehydes, alcohols and other chemical entities with standard reduction potentials greater than about -0.42 V relative to the standard hydrogen electrode (SHE). The standard reduction potentials of chromium in acidic solution are:
Cr2O7 2" 0.55 Cr(V) 1.34 Cr(IV) 2.10 Cr(III) -0.424 Cr(II) -0.90 Cr(O)
In another embodiment of the present invention, (1) and/or (2) may be used as a catalyst. For example, the cobalt(ll) analog, [Co"(CN)5]3~, has shown reactivity in hydrogenation, carbonylation and reactions with organic halides. Additionally, the unsaturated nature of the cyanochromate complexes provides the opportunity for substrates to bind to the chromium center with relatively little steric or electronic repulsion from neighboring ligands. Upon binding to the metal, the substrate may become activated toward other nearby substrates. Following the reaction with a nearby substrate, the metal may release the bound substrate into solution and become available for further substrate transformations. In a particular embodiment, (1) and/or (2) may catalyze a polymerization reaction where monomers react to form polymer chains. The catalysts may operate under homogeneous or heterogeneous conditions, and it may be desirable or necessary to add co-catalysts or initiators, as described in the art.
In another embodiment of the present invention, (1) and/or (2) may be used as a building block in the synthesis of molecule-based magnetic materials with the general formulas M'"[Cr"(CN)5] (3), M11M111CCr1^(CN)9] (4), M"3[Cr"(CN)5]2 (5) and the like, where ancillary cations, anions and/or salvation molecules may be present. Such materials may be synthesized, for example, by the methods shown in Schemes 1-3 below:
Scheme 1 [NEt4]3_Cr"(CN)5] (1) + [Cr111CMeCN)6](BF4)S → Crlll[Crll(CN)5] (3) + 3 NEt4BF4
Scheme 2
[NEU]5[Cr11S(CN)9] (2) + [Cr111IMeCN)6](BF4)S + [Fe"(MeCN)6](BF4)2 →
Fe11Cr111ICr11Z(CN)9] (4) + 5 NEt4BF4
Scheme 3 2 [NEt4]3[Cr"(CN)5] (1) + 3 [M"(MeCN)6](BF4)2 → Mll 3[Cr"(CN)5]2 (5) + 6 NEt4BF4
Various metal (M", M1") sources may be substituted in the above reactions. One of skill in the art will readily be able to identify suitable reagents.
In a particular embodiment, [NEt4]3[Cr"(CN)5] (1) is used as a building block for a magnetic material with the formula M"'[Cr"(CN)5] (3), which may be accomplished for example by dissolving one equivalent of a M1" source, such as
Figure imgf000005_0001
and adding it dropwise to one equivalent of [NEt4]3[Cr"(CN)5] (1) dissolved in the same solvent to form the polymeric magnetic material MlM[Cr"(CN)5]
(3).
In a particular embodiment,
Figure imgf000005_0002
(2) is used as a building block for a magnetic material with the formula M11M111ICr1^(CN)9] (4), which may be accomplished for example by dissolving one equivalent of a M1" source, such as Mlll(MeCN)6(BF4)2, and adding it dropwise to one equivalent of
Figure imgf000005_0003
(2) dissolved in the same solvent to form the polymeric magnetic material
M11M111CCr11S(CN)9] (4).
In a particular embodiment, [NEt4]3[Cr"(CN)5] (1) is used as a building block for a magnetic material with the formula M"3[Crn(CN)5]2 (5), which may be accomplished for example by dissolving one equivalent of a M1" source, such as
M111CMeCN)6(BF4)S, and adding it dropwise to one equivalent of [NEt4]3[Cr"(CN)5] (1) dissolved in the same solvent to form the polymeric magnetic material M"3[Cr"(CN)5]2
(5). Definitions:
For the purposes of the present invention, the following terms shall have the following meanings:
For the purposes of the present invention, the terms "chromium(ll)", "Cr(II)", "Cr2+" and "Cr"" may be used interchangeably to describe divalent chromium or a chromium metal atom that has lost two electrons.
For the purposes of the present invention, the term "ligand" shall refer to an organic species that binds to one or more metal cations. A ligand may form a bridge between two or more metal cations. Ligands, in general, are negatively charged species (e.g., CN') or uncharged species presenting a lone electron pair that interacts electrostatically with a metal cation (e.g., MeCN).
For the purposes of the present invention, the term "coordinatively unsaturated" shall be used to refer to a metal complex that contains fewer than the theoretically allowed number of ligands, as determined by the metal orbitals available for bonding. While 7 ligands may bond to Cr(II), typically, a transition metal is considered saturated if it is surrounded by 6 ligands; thus, a transition metal complex containing 5 or fewer ligands may be considered coordinatively unsaturated.
For the purposes of the present invention, the term "counterion" shall refer to an organic cation that does not tightly bind a corresponding anion, in this case the cyanochromates. Counterions are typically large so that charge may be widely distributed. Exemplary counterions include tetramethylammonium (NMe4 +), tetraethylammonium (NEt4 +), tetrapropylammonium (NPr4 +), f-butylammonium (TBA), tetraphenylphosphonium (PPh4 +), tetraphenylarsonium (AsPh4 +), methyltriphenylphosphonium (Ph3MeP+), methyltriphenylarsonium (Ph3MeAs+), methyl pyridinium (Me(S-X)C5HxNH+) and the like.
For the purposes of the present invention, the term "Cr" source" shall refer to a reactant containing at least one Cr atom in a 2+ or (II) oxidation state. Chromium(ll) from the "Cr" source" will be incorporated into the final product. In the preparation of (1) and (2) a Cr" source typically contains large, negatively charged anions or ligands (e.g., BF4 ", OAc', BARF", CIO4 ") that may be easily replaced by cyanide (CN"). In the preparation of molecule-based magnets where (1) or (2) is a building block, (1) or (2) itself would be the "Cr" source" that becomes incorporated into the final product and a separate "metal source" may be used to incorporate various other metals (M). Moreover, for the purposes of the present invention, the term "a" or "an" entity refers to one or more than one of that entity; for example, "a metal" or "an anion" refers to one or more of those compounds, or at least one compound. As such, the terms "a" or "an", "one or more" and "at least one" can be used interchangeably herein. It is also to be noted that the terms "comprising", "including", and "having" can be used interchangeably. Furthermore, a compound "selected from the group consisting of refers to one or more of the compounds in the list that follows, including mixtures (i.e., combinations) of two or more of the compounds.
EXAMPLES
The following examples are included to demonstrate particular embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention, and thus can be considered to constitute particular modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still a like or similar result will be obtained without departing from the spirit and scope of the invention.
Experimental Parameters
All experiments were carried out in a VacAtm inert atmosphere drybox with dry, deoxygenated solvents. NEt4CN was prepared by reacting NaCN and NEt4CI in
MeOH followed by extraction/crystallization in MeCN. Cr"2(OAc)4 was prepared by a
Zn(Hg) oxidation of Cr metal, followed by addition of the Cr2+ solution to a saturated solution of sodium acetate. [Cr"(NCMe)4][BF4]2 was prepared by suspending
Cr2(OAc)4 in a 1:2 volumetric ratio of MeCN:CH2CI2 to which a excess amount of
HBF4 Et2O was slowly added with vigorous stirring. Upon completion of the reaction, the solution was taken to dryness and redissolved in a minimal amount of MeCN.
The solution was then filtered and the product was crystallized at about -15°C.
Example 1: Synthesis and characterization of [NEt4]3[Cr"(CN)5]«MeCN*1/8THF
Cr"2(OAc)4 (112.11 mg, 0.3296 mmol, 1.00 eq.) dissolved in 75 mL of MeCN, or [Cr"(NCMe)4][BF4]2 (299.7 mg, 0.7688 mmol, 1.00 eq.) dissolved in 15 mL of MeCN, was added dropwise to approximately 25 mL of stirring MeCN solution containing NEt4CN (622.80 mg, 3.985 mmol, 12.09 eq. for Cr"2(OAc)4) or (721.30 mg, 4.616 mmol, 6.00 eq. for [Cr"(NCMe)4][BF4]2). The combined solution was stirred for 30 minutes, filtered and concentrated to 30 mL under reduced pressure. The dark red crystalline product was isolated by THF diffusion and characterized by single crystal X-ray diffractometry, solid state infrared (IR) spectrometry (KBr), UV- visible absorption spectroscopy and magnetization studies. Heating at about 1100C under vacuum, [NEU]3[Cr"(CN)5]-MeCN»1/8THF forms desolvated [NEUk[Cr"(CN)5]. In this way materials with differing degrees of desolvation may be prepared and isolated.
The crystal structure is triclinic, Pi , a = 17.8172(3) A, b = 20.8318(6) A, c = 21.5756(5) A, α = 87.6399(9)°, β = 87.6399(9)°, γ = 84.4486(13)° Both square pyramidal and distorted trigonal bipyramid structures are present in the unit cell. IR: υc=N 2086 cm'1. Beer's law is not obeyed in the electronic absorption spectrum (22,120 cm"1 (452 nm; ε = 122 M"1 cm"1, 1.30 mM solution). μΘff « 4.9 μB consistent with high spin d4 Cr(II), S = 2.
Example 2: Synthesis and characterization of [NEU]8[Cr"(CN)5][Cr"2(CN)9]'2MeCN, containing [NEUk[Cr11CCN)5] and [NEU]5[Cr1^(CN)9] Cr"2(OAc)4 (55.94 mg, 0.1644 mmol, 1.00 eq.) was dissolved in 40 mL of
MeCN to form a light red solution, which was then added dropwise to a clear, colorless stirring solution of NEUCN (256.3 mg, 1.640 mmol, 9.972 eq.) dissolved in 25 mL MeCN. The resulting reddish purple solution was stirred for 30 minutes, filtered and concentrated to 30 mL under reduced pressure. The product crystallized from the solution as brown needles following three weeks of vapor diffusion with THF. The crystals were analyzed by single crystal X-ray diffractometry, solid state IR spectrometry (KBr). Heating [NEU]β[Crll(CN)5][Crll 2(CN)9]«2MeCN forms desolvated [NEU]8[Cr"(CN)5][Crll 2(CN)9]. In this way materials with differing degrees of desolvation may be prepared and isolated. The crystal structure is triclinic, Pi , a = 10.2618(2) A, b = 22.4902(5) A, c =
23.4526(4) A, α = 114.5636(8)°, β = 90.3961(11)°, γ = 101.8783(10)° Both the monomeric and dimeric chromium sites are square pyramidal. IR: UC=N 2090 cm"1. Example 3: Use of (1) and/or (2) as a reducing agent
To a stirring solution containing a compound to be reduced, a solution of (1) and/or (2) may be added by separatory funnel, cannula, syringe or other known means. The reaction vessel may be cooled or heated as necessary and the progress of the reaction may be monitored by thin layer chromatography (TLC), for example. Upon completion of the reaction, the product may be isolated from side- products and/or remaining starting material by silica gel chromatography, crystallization or other available means.
Example 4: Use of (1) and/or (2) as a catalyst
To a stirring solution of cyclopropene, a catalytic amount of (1) and/or (2) dissolved in a minimal amount of solvent is added. A co-catalyst and/or initiator are optionally added. (1) and/or (2) catalyze the conversion of cyclopropene to polypropylene.
Example 5: Use of (1) as a building block for a magnetic material with the formula M111ICr11CCN)5] (3)
One equivalent of a M1" source, such as M'"(MeCN)6(BF4)3, may be dissolved in a suitable solvent (e.g., MeCN, THF, CH2CI2). The solution is stirred for 10-30 minutes and then filtered. In a second flask, one equivalent of [NEt4]3[Cr"(CN)5] (1) is dissolved, preferably using the same solvent as that used for the M1" source. The solution containing M'"(MeCN)6(BF4)3 is added dropwise to the pentacyanochromate solution with constant stirring. The polymeric magnetic material formed, M'"[Cr"(CN)5], will precipitate and may be collected by filtration and washed to remove impurities.
Example 6: Use of (2) as a building block for a magnetic material including M11M111ICr1^(CN)9] (4)
A M1" source, such as M"'(MeCN)6(BF4)3, and a M11 source, such as M"(MeCN)6(BF4)2, may be dissolved in a single flask using a suitable solvent (e.g.,
MeCN, THF, CH2CI2). The solution is stirred for 10-30 minutes and then filtered. In a second flask, a compound containing [NEt4]5[Cr"2(CN)9] (2) is dissolved, preferably using the same solvent as that used for the M sources. The M'VM'" solution is added dropwise to the nonacyanodichromate solution with constant stirring. The polymeric magnetic material formed, which includes M11M111ICr1^(CN)9], will precipitate and may be collected by filtration and washed to remove impurities.
Example 7: Use of (1) as a building block for a magnetic material with the formula M"3[Cr"(CN)5]2 (5)
Three equivalents of a M" source, such as M"(MeCN)6(BF4)2 may be dissolved in a suitable solvent (e.g., MeCN, THF, CH2CI2). The solution is stirred for 10-30 minutes and then filtered. In a second flask, two equivalents of [NEt4]3[Cr"(CN)5] (1) are dissolved, preferably using the same solvent as that used for the M source. The Mn solution is added dropwise to the pentacyanochromate solution with constant stirring. The polymeric magnetic material formed, M"3[Cr"(CN)5]2, will precipitate and may be collected by filtration and washed to remove impurities.
All of the COMPOSITIONS, METHODS and APPARATUS disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the COMPOSITIONS, METHODS and APPARATUS and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
Glossary
MeCN acetonitrile, CH3CN
THF tetrahydrofuran, C4H8O
Et ethyl
Me methyl
Pr propyl
OAc acetate
BARF tetrakis(3,5-trifluoromethylphenyl)borate

Claims

We Claim:
1. A composition comprising a pentacyanochromate(ll).
2. The composition of claim 1 , wherein the pentacyanochromate(ll) is [NEU]3[Cr"(CN)5].
3. A catalyst comprising the composition of claim 1.
4. A reducing agent comprising the composition of claim 1.
5. A magnetic material comprising the composition of claim 1.
6. A composition comprising a nonacyanochromate(ll).
7. The composition of claim 6, wherein the nonacyanochromate(ll) is
[NEt4]5[Crll 2(CN)9].
8. A catalyst comprising the composition of claim 6.
9. A reducing agent comprising the composition of claim 6.
10. A magnetic material comprising the composition of claim 6.
11. A method of forming a magnetic material comprising: a. dissolving a M1" source in a solvent, b. dissolving a pentacyanochromate(ll) in said solvent, c. adding said dissolved pentacyanochromate(ll) to said dissolved M1" source to form a polymeric magnetic material.
12. A magnetic material created using the method of claim 11.
13. The method of claim 11 wherein said polymeric magnetic material is selected from the group consisting of M111ICr1^CN)5] and M"3[Cr"(CN)5]2.
14. The method of claim 11 wherein said pentacyanochromate(ll) is [NEt4MCr11CCN)5].
15. A method of forming a magnetic material comprising: a. dissolving a M1" source in a solvent, b. dissolving a nonacyanochromate(ll) in said solvent, c. adding said dissolved nonacyanochromate(ll) to said dissolved M1" source to form a polymeric magnetic material.
16. A magnetic material created using the method of claim 15.
17. The method of claim 15 wherein said polymeric magnetic material is MllMlll[Crll 2(CN)9].
18. The method of claim 15 wherein said nonacyanochromate(ll)is
Figure imgf000013_0001
PCT/US2005/039771 2004-11-04 2005-11-04 Pentacyanochromate(ii) and nonacyanodichromate(ii) compositions and uses thereof WO2006057785A2 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995555A (en) * 1958-08-04 1961-08-08 Diamond Alkali Co Chromate derivatives

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995555A (en) * 1958-08-04 1961-08-08 Diamond Alkali Co Chromate derivatives

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