The ethene complex trans-[IrCl(C2H4) (ASiPr(3))(2)] (2), which was prepared from [IrCl(C2H4)(2)](2) and AsiPr(3), reacted with CO and Ph2CN2 by displacement of ethene to yield the substitution products trans-[IrCl(L) (ASiPr(3))(2)] (3: L = CO; 4: L = N-2) UV irradiation of 2 in the presence of acetonitrile gave via intramolecular oxidative addition the hydrido(vinyl) iridium(III) compound [IrHCl(CH=CH2)(CH3CN)(AsiPr(3))(2)] (5). The reaction of 2 with dihydrogen led under argon to the formation of the octahedral complex [IrH2Cl(C2H4)(AsiPr(3))(2)] (7), whereas from 2 under 1 bar H-2 the ethene-free compound [IrH2Cl(AsiPr(3))(2)] (6) was generated. Complex 6 reacted with ethene to afford 7 and with pyridine to give [IrH2Cl(py)(AsiPr(3))(2)] (8). The mixed arsane(phosphane)iridium(I) compound [IrCl(C2H4)(PiPr(3))-(AsiPr(3))] (11) was prepared either from the dinuclear complex [IrCl(C2H4)(PiPr(3))](2) (9) and AsiPr(3) or by ligand exchange from [IrCl(C2H4)(PiPr(3)) (SbiPr(3))] (10) und triisopropylarsane. The molecular structure of 5 was determined by X-ray crystallography.
Stable Carbeneiridium(I) Complexes with 16- and 18-Electron Configurations at the Metal Center
作者:Dagmara A. Ortmann、Birgit Weberndörfer、Jan Schöneboom、Helmut Werner
DOI:10.1021/om980984p
日期:1999.3.1
Using the mixed phosphine-stibine compound [IrCl(C2H4)(PiPr(3))(SbiPr(3))] (2) as the starting material, the square-planar carbeneiridium(I) complexes [IrCl(=CR2),(PiPr(3))(SbiPr(3))] (3a,b) and trans-[IrCl(= CR2)(PiPr(3))(2)] (4a,b) were prepared. The cyclopentadienyl derivative [C5H5Ir(=CPh2)(PiPr(3))] (5), obtained from 3a and NaC5H5, reacts with HCl by attach of the Ir=CPh2 bond; in, contrast, upon treatment of 4a with HCl or HBF4, hydridoiridium(lll) complexes 8 and 9 with art intact Ir=CPh2 unit are formed.