CN105237579A - Platinum complex crystal - Google Patents
Platinum complex crystal Download PDFInfo
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- CN105237579A CN105237579A CN201510795302.7A CN201510795302A CN105237579A CN 105237579 A CN105237579 A CN 105237579A CN 201510795302 A CN201510795302 A CN 201510795302A CN 105237579 A CN105237579 A CN 105237579A
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- platinum
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- complex crystal
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Abstract
The invention discloses a platinum complex crystal with the following structural formula as shown in the description. A synthesis method of the complex crystal comprises the steps of carrying out reflux reaction for 60 hours by taking 1.2042g of platinum chloride, 10mL of DMSO and 30mL of dichloromethane as solvents; purifying, carrying out thermal filtration, and preparing a saturated solution from dichloromethane and petroleum ether according to the volume ratio of 1:1; and naturally volatizing to obtain a dimethylsulfoxide platinum complex monocrystal. The complex has favorable catalytic performances in cyano-silicification reaction of benzaldehyde and has the conversion ratio of 39%.
Description
one, technical field
The present invention relates to a kind of organometallic complex (title complex) and preparation method thereof, particularly oxygen metal organic coordination compound and preparation method thereof, is exactly a kind of methyl-sulphoxide platinum nitrate complex crystal and synthetic method thereof.
two, background technology
Metal platinum complex to have caused the extensive concern of people because of it in the potential using value in anticancer and molecular magnet, fluorescent material etc.The synthetic method of metal platinum complex has many bibliographical informations in recent years: [1-7]
1.AComparativeAntimicrobialStudyInBetweenaQuinolineDrugandItsComplexes:Spectral,Kinetic,andMolecularModelingInvestigations,Al-Hazmi,GamilA.A.;Saad,FawazA.SynthesisandReactivityinInorganic,Metal-Organic,andNano-MetalChemistry(2015),45(11),1743-1757.
2.One-?potsynthesisofdual-?emittingBSA-?Pt-?Aubimetallicnanoclustersforfluorescenceratiometricdetectionofmercuryionsandcysteine,Ding,Shou-Nian;Guo,Yun-Xia
FromAnalyticalMethods(2015),7(14),5787-5793.
3.Fivecoordinateplatinum(II)in[Pt(bpy)?(cod)?(Me)?]?[SbF6]?:astructuralandspectroscopicstudy,Klein,Axel;Neugebauer,Michael;Krest,Alexander;Luening,Anna;Garbe,Simon;Arefyeva,Natalia;Schloerer,Nils,Inorganics(2015),3(2),118-138.
4.SynthesisandReactivityofPlatinum(II)cis-?Dialkyl,cis-?AlkylChloro,andcis-?AlkylHydridoBis-?N-?heterocyclicCarbeneChelateComplexes,Brendel,Matthias;Engelke,Rene;Desai,VidyaG.;Rominger,Frank;Hofmann,Peter,Organometallics(2015),34(12),2870-2878.
5.TheChallengeofDecipheringLinkageIsomersinMixturesofOligomericComplexesDerivedfrom9-?Methyladenineandtrans-?(NH3)?2PtIIUnits,Ibanez,Susana;Mihaly,Bela;SanzMiguel,PabloJ.;Steinborn,Dirk;Pretzer,Irene;Hiller,Wolf;Lippert,Bernhard
Chemistry-AEuropeanJournal(2015),21(15),5794-5806.
6.PolypyridylrutheniumcomplexescontaininganchoringnitrilegroupsasTiO2sensitizersforapplicationinsolarcells,MecchiaOrtiz,JuanH.;Longo,Claudia;Katz,NestorE.InorganicChemistryCommunications(2015),55,69-72.
7.Charge-?bistablePd(III)?/Pd(II,?IV)coordinationpolymers:phasetransitionsandtheirapplicationstoopticalproperties,Kumagai,Shohei;Takaishi,Shinya;Iguchi,Hiroaki;Yamashita,Masahiro,DaltonTransactions(2015),44(18),8590-8599。
three, summary of the invention
The present invention aims to provide a kind of Pt-O a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected methyl-sulphoxide as part and synthesized methyl-sulphoxide platinum chloride title complex.
Platinum complex alleged by the present invention is a kind of be by methyl-sulphoxide dimethyl sulfide platinum chloride title complex and Silver Nitrate prepare by the title complex shown in following chemical formula:
（Ⅰ）
Chemical name: methyl-sulphoxide dimethyl sulfide platinum nitrate title complex title complex, is called for short title complex (I).
This title complex shows good catalytic performance in the nitrile silicification reaction of phenyl aldehyde, and its transformation efficiency is 39%.
This synthetic method comprises synthesis and is separated, described synthesis 0.3521g methyl-sulphoxide dimethyl sulfide platinum chloride, 0.5135g silver chloride, solvent is made with 20mL methylene dichloride, aluminium-foil paper lucifuge room temperature does reaction 30 hours, filter, be 1/1 obtain solution by methylene dichloride/trichloromethane volume ratio, volatilize to obtain methyl-sulphoxide dimethyl sulfide platinum nitrate complex monocrystal naturally.
Building-up reactions is as follows:
This synthetic method one step obtains target product, and technique is simple, easy to operate.
Four, accompanying drawing explanation
The X-diffraction analysis figure that Fig. 1 methyl-sulphoxide platinum chloride coordinates.
[five, embodiment
0.3521g methyl-sulphoxide dimethyl sulfide platinum chloride is added in two-mouth bottle, 0.5135g silver chloride, solvent is made with 20mL methylene dichloride, aluminium-foil paper lucifuge room temperature does reaction 30 hours, filter, be 1/1 obtain solution by methylene dichloride/trichloromethane volume ratio, volatilize to obtain methyl-sulphoxide dimethyl sulfide platinum nitrate complex monocrystal naturally; Productive rate 48%, fusing point: 142-146 ° C; Ultimate analysis: test value: C:11.43%, H:2.97%; N:5.77% calculated value: C:10.46%, H2.63%, N:6.10%; IR (KBr): 3020,2923,1527,1505,1384,1274,1259,1159,1024,965,918,794,448; Match crystal volume data is as follows:
Empirical formula C4H12N2O7PtS2
Molecular weight 459.37
Temperature 296 (2) K
Wavelength 0.71073
Crystallographic system, Space group Monoclinic system, Pbca
Unit cell parameters a=12.9484 (4) α=90 °.
b=11.644(4)?β=90°.
c=16.134(5)?γ=90°.
Volume 2432.3(13) ^3
Electric density 8,2.509Mg/m^3
Absorption correction parameter 11.901mm^-1
Number of electrons 1728 in unit cell
Crystallographic dimension 0.140x0.130x0.090mm
The scope 2.525to25.999 at Theta angle
Index capture range-the 14<=h<=15 of HKL ,-14<k<14 ,-19<l<=19
Collection/independent diffraction data 16343/2391 [R (int)=0.0468]
The data integrity degree 100.0% of theta=30.5
The method Multi Slice Mode of absorption correction
The transmitance 0.7456and0.4194 of minimax
The Matrix least square method of the method F^2 that refine uses
Number/the number of parameters 2391/0/149 of data number/use restriction
The method 1.059 that refine uses
The consistence factor R 1=0.0243 of point diffraction, ω R2=0.0496
Identical factor R 1=0.0429, the ω R2=0.0568 of observable diffraction
Maximum summit on difference Fourier figure and peak valley 1.084and-0.567e. ^-3
the typical bond distance's data of crystal:
Pt(1)-O(5)2.039(5)
Pt(1)-O(2)2.047(4)
Pt(1)-S(1)2.1955(18)
Pt(1)-S(2)2.2576(16)
S(1)-O(1)1.445(5)
S(1)-C(2)1.752(6)
S(1)-C(1)1.752(7)
S(2)-C(4)1.780(7)
S(2)-C(3)1.796(7)
C(1)-H(1A)0.9600
C(1)-H(1B)0.9600
C(1)-H(1C)0.9600
C(2)-H(2A)0.9600
C(2)-H(2B)0.9600
C(2)-H(2C)0.9600
C(3)-H(3A)0.9600
C(3)-H(3B)0.9600
C(3)-H(3C)0.9600
C(4)-H(4A)0.9600
C(4)-H(4B)0.9600
C(4)-H(4C)0.9600
N(1)-O(3)1.209(7)
N(1)-O(4)1.212(6)
N(1)-O(2)1.307(6)
N(2)-O(6)1.210(7)
N(2)-O(7)1.217(7)
N(2)-O(5)1.313(7)
the typical bond angle data of crystal:
O(5)-Pt(1)-O(2)86.19(18)
O(5)-Pt(1)-S(1)174.95(13)
O(2)-Pt(1)-S(1)89.09(13)
O(5)-Pt(1)-S(2)95.77(13)
O(2)-Pt(1)-S(2)171.25(13)
S(1)-Pt(1)-S(2)89.16(6)
O(1)-S(1)-C(2)108.2(3)
O(1)-S(1)-C(1)109.7(4)
C(2)-S(1)-C(1)102.7(4)
O(1)-S(1)-Pt(1)116.8(2)
C(2)-S(1)-Pt(1)111.8(2)
C(1)-S(1)-Pt(1)106.7(3)
C(4)-S(2)-C(3)99.9(4)
C(4)-S(2)-Pt(1)109.9(3)
C(3)-S(2)-Pt(1)106.1(3)
S(1)-C(1)-H(1A)109.5
S(1)-C(1)-H(1B)109.5
H(1A)-C(1)-H(1B)109.5
S(1)-C(1)-H(1C)109.5
H(1A)-C(1)-H(1C)109.5
H(1B)-C(1)-H(1C)109.5
S(1)-C(2)-H(2A)109.5
S(1)-C(2)-H(2B)109.5
H(2A)-C(2)-H(2B)109.5
S(1)-C(2)-H(2C)109.5
H(2A)-C(2)-H(2C)109.5
H(2B)-C(2)-H(2C)109.5
S(2)-C(3)-H(3A)109.5
S(2)-C(3)-H(3B)109.5
H(3A)-C(3)-H(3B)109.5
S(2)-C(3)-H(3C)109.5
H(3A)-C(3)-H(3C)109.5
H(3B)-C(3)-H(3C)109.5
S(2)-C(4)-H(4A)109.5
S(2)-C(4)-H(4B)109.5
H(4A)-C(4)-H(4B)109.5
S(2)-C(4)-H(4C)109.5
H(4A)-C(4)-H(4C)109.5
H(4B)-C(4)-H(4C)109.5
O(3)-N(1)-O(4)123.5(6)
O(3)-N(1)-O(2)119.7(5)
O(4)-N(1)-O(2)116.8(6)
O(6)-N(2)-O(7)123.9(7)
O(6)-N(2)-O(5)119.6(6)
O(7)-N(2)-O(5)116.5(7)
N(1)-O(2)-Pt(1)117.9(4)
N(2)-O(5)-Pt(1)116.9(4)
Six, nitrile silicification reaction application
2-phenyl-2-(three silyloxy) propionitrile
0.1mmol title complex I, phenyl aldehyde 0.1mL, TMSCN0.3ml (3.3mmol); 2mL anhydrous methanol, adds in succession under 30 ~ 35 C, after 96 hours; add shrend and go out after post layer that (sherwood oil/methylene dichloride: 5/1), obtains colourless oil liquid, transformation efficiency: 39%;
1hNMR (300MHz, CDCl3) 7.56 – 7.59 (m, 0.9Hz, 2H), 7.31 – 7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H).
13cNMR (75MHz, CDCl3) 136.1,128.8 (x2), 126.2 (x2), 119.1,63.5 ,-0.39 (x3).
Claims (3)
1. a platinum complex crystal, its structural formula is as follows:
（Ⅰ）
。
2. platinum complex crystal according to claim 1; at 296 (2) K temperature; on the X-ray single crystal diffraction instrument of Oxford; with MoK alpha-ray λ=0.71073 through graphite monochromator monochromatization; diffraction data is collected with ω-θ scan mode; it is characterized in that crystal belongs to rhombic system, spacer Pbca, unit cell parameters a=12.9484 (4) α=90 °; B=11.644 (4) β=90 °; C=16.134 (5) γ=90 °.
3. the synthetic method of platinum complex crystal according to claim 1, comprise synthesis and be separated, described synthesis 0.3521g methyl-sulphoxide dimethyl sulfide platinum chloride, 0.5135g silver chloride and 20mL methylene dichloride make solvent, aluminium-foil paper lucifuge room temperature did reaction after 30 hours, filter, be 1/1 obtain solution by methylene dichloride/trichloromethane volume ratio, volatilize to obtain methyl-sulphoxide dimethyl sulfide platinum nitrate complex monocrystal naturally.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001268A (en) * | 2015-08-13 | 2015-10-28 | 合肥祥晨化工有限公司 | Crystals of chiral oxazoline platinum complex and synthesize method of crystals |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001268A (en) * | 2015-08-13 | 2015-10-28 | 合肥祥晨化工有限公司 | Crystals of chiral oxazoline platinum complex and synthesize method of crystals |
Non-Patent Citations (4)
| Title |
|---|
| MASATO UEMURA 等: "Enantioselective Cyanosilylation of Ketones with Amino Acid/BINAP/Ruthenium(II)-Lithium Phenoxide Catalyst Systems", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| PRAMESH KAPOOR 等: "Cis/trans influences in platinum(II) complexes.X-ray crystal structures of cis-dichloro(dimethyl sulfide)(dimethyl sulfoxide)platinum(II) and cis-dichloro(dimethyl sulfide)(dimethyl phenyl phosphie)platinum(II)", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
| XIANG-GE ZHOU: "Titanium and ruthenium binaphthyl Schiff base complexes as catalysts for asymmetric trimethylsilylcyanation of aldehydes", 《J.CHEM.SOC.,DALTON TRANS.》 * |
| 傅颖 等: "醛酮的不对称硅氰化反应研究进展", 《有机化学》 * |
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Application publication date: 20160113 |