Oxidative-addition and reductive-elimination reactions of carboraneiridium complexes

✍ Scribed by B. Longato; F. Morandini; S. Bresadola

• Publisher: Elsevier Science
• Year: 1980
• Tongue: English
• Weight: 761 KB
• Volume: 39
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)93629-6

✦ Synopsis

The addition reactions of diatomic molecules, X-Y (X-Y = HCl, HBr, HI, Cl? and BrJ to squareplanar d0 carborane-iridium(I) complexes of general formula trans-[Ir(o-carb)(CO)L,], where L = PPh3, PMePhz and carb = -2-R-1,2-and -7-R-I,7-BlO-CzHlo (R = H, CH,, CJI,) have been investigated in both the solid state and in solution of a variety of solvents. The stereochemistry of the obtained octahedral adducts was determined by i.r. and 'H nmr spectroscopy. The stereochemical course of the addition reactions appears to be dependent on the reaction medium and on the type of the carborane anionic ligands. Evidence suggesting that these oxidativeaddition reactions proceed through solventcontaining intermediates when they are carried out in coordinating solvents is reported. I%e HX adducts of general formula [Ir(H)(X)(ocarb)(CO)Lz] , (X = Cl, Br, I), reductively eliminate the carborane molecule, H-carb. Factors governing

these elimination reactions are also described.