Luminescent Iridium(I) Diethyldithiocarbamate Complexes: Synthesis, Structure, and Reactivity Including Stereoselective Hydrogen Oxidative Addition
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- 作者：Gianfranco Suardi ; Brian P. Cleary ; Simon B. Duckett ; Christopher Sleigh ; Melinda Rau ; Earl W. Reed ; Joost A. B. Lohman ; and Richard Eisenberg
- 刊名：Journal of the American Chemical Society
- 出版年：1997
- 出版时间：August 20, 1997
- 年：1997
- 卷：119
- 期：33
- 页码：7716 - 7725
- 全文大小：315K
- 年卷期：v.119,no.33(August 20, 1997)
- ISSN：1520-5126
文摘
A series of neutral Ir(I) complexesIrLL'(EtB>2dtc) (L = L' = CO PPh3,P(OPh)3; L = CO, L' = PPh3; L+ L' = 1,2-bis(diphenylphosphino)ethane,1,5-cyclooctadiene,1,2-bis(di(pentafluorophenyl)phosphino)ethane;Et2dtc = N,N'-diethyldithiocarbamate) has beensynthesized and characterized by NMR, IR, and electronicspectroscopies.The complexes show spectra consistent with a four-coordinatestructure. A distorted square planar coordinationgeometry is confirmed by a single crystal structure determination ofIr(CO)(PPh3)(Et2dtc)(3). Yellow-orange crystalsof 3(C24H25IrNOPS2) aremonoclinic, space group P21/n (no.14), with a = 15.641(12) Å, b =9.252(3) Å, c =17.119(14) Å, 
beta2.gif" BORDER=0 ALIGN="middle"> = 111.42(3)
, V = 2395.00Å3, Z = 4, and final R = 0.029(Rw = 0.031) for 3204 uniquereflections.All of the complexes exhibit emission in the solid state and infrozen glass media at 77 K. Additionally,Ir(CO)(PPh3)(Et2dtc),Ir(dppe)(Et2dtc), andIr(P(OPh)3)2(Et2dtc)display emission in methylene chloride solutions at roomtemperature. The bis triphenylphosphite complex,Ir(P(OPh3)2)(Et2dtc),undergoes intramolecular C-H activationin benzene solution to form the ortho-metalated productIr(P(OPh)2(OC6H4))(H)(P(OPh)3)(Et2dtc). A benzene solutionof Ir(CO)(PPh3)(Et2dtc) reactsreadily with H2, forming several different dihydrideproducts having the formulaIrH2(CO)(PPh3)(Et2dtc),including an isomer with a kinetic preference for formation of 170:1 asdetermined usingparahydrogen induced polarization (PHIP) at 300 K. A method isdescribed for observing the 13C resonance ofthecarbonyl ligand in submilligram samples ofIrH2(PPh3)(CO)(Et2dtc) in under 2min. The ligand exchange reactionsof the two parahydrogen active isomers are also examined. PHIP isalso observed in H2 oxidative addition toIr((C6F5)2PCH2CH2P(C6F5)2)(Et2dtc).Benzene solutions ofIr(CO)(PPh3)(Et2dtc) andIr(dppe)(Et2dtc) react withmolecularoxygen to form the stable adductsIr(O2)(CO)(PPh3)(Et2dtc)and Ir(O2)(dppe)(Et2dtc),respectively, and both lose O2upon irradiation only. The complexIr(CO)(PPh3)(Et2dtc) oxidatively addsCH3I to form the trans addition productIr(CH3)(CO)(I)(PPh3)(Et2dtc).
beta2.gif" BORDER=0 ALIGN="middle"> = 111.42(3), V = 2395.00Å3, Z = 4, and final R = 0.029(Rw = 0.031) for 3204 uniquereflections.All of the complexes exhibit emission in the solid state and infrozen glass media at 77 K. Additionally,Ir(CO)(PPh3)(Et2dtc),Ir(dppe)(Et2dtc), andIr(P(OPh)3)2(Et2dtc)display emission in methylene chloride solutions at roomtemperature. The bis triphenylphosphite complex,Ir(P(OPh3)2)(Et2dtc),undergoes intramolecular C-H activationin benzene solution to form the ortho-metalated