
TY  - JOUR
A1  - Bennett, MA 
A1  - Crisp, GT 
T1  - Oxidative Addition of Functionalized Alkyl-Halides to Iridium(I) Complexes IrCl(Co)L<sub>2</sub> (L = PMe<sub>2</sub>Ph<sub>2</sub>>, IrCl(Co)PMe<sub>3</sub>)
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1986
VL  - 39
IS  - 9
SP  - 1363
EP  - 1375
KW  - 
UR  - https://doi.org/10.1071/CH9861363 
N2  - Iridium(I) complexes IrCl (CO)L2 (L = PMePh2, PMe2Ph, PMe3) oxidatively add alkyl bromides RBr bearing electron-withdrawing substituents on the &#945;-carbon atom (R = CH2CO2Et,CH3CHCO2Et,CH3CHCOCH3,C2H5CHNO2) to give octahedrally coordinated alkyliridium (III) complexes IrBrClR (CO)L2, for which 1H and 31P n.m.r . data are reported. In the secondary alkyls, the mutually trans tertiary phosphine ligands are inequivalent, consequently the P-Me resonance is not the usual 1 : 2 : 1 'virtual' triplet. In some cases the pattern is a doublet or a doublet of doublets, similar to that expected for mutually cis tertiary phosphine  ligands . In contrast to simple s- alkyliridium (III) complexes, the functionalized s-alkyls do not isomerize under any conditions to the corresponding n-alkyls, and the reverse process does not occur for n-alkyls such as IrBrCl (CH2CH2CO2Et)(CO)(PMe3)2 and IrClI (CH2CH2CN)(CO)(PMe3)2. Diiodomethane and chloroiodomethane readily add to IrCl (CO)L2 to give haloalkyliridium (III) complexes IrClI (CH2Y)(CO)L2(Y = Cl , I). These contain mutually trans tertiary phosphine  ligands , although in the case of L = PMe2Ph unstable cis - isomers can be detected. Attempts to form complexes containing Ir - CHBrCH3 or Ir -CH(OC2H5)CH3 by addition of CH3CHBr2 or CH3CHClOC2H5 to IrCl (CO)(PMe3)2 gave only IrBr2Cl(CO)(PMe3)2 and IrHCl2(CO)(PMe3)2, respectively. 
ER  -

