Structure and bonding analysis of dimethylgallyl complexes of cobalt, rhodium and iridium [Me(PMeub>3ub>)ub>2ub>(Meub>3ub>GaCl)M(GaMeub>2ub>)] (M聽=聽Co, Rh, Ir) and [Me(PMeub>3ub>)ub>2ub>ClIr(GaMeub>2ub>)]: A theoretica

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• 作者：Krishna K. Pandey ; ^{kkpandey.schem@dauniv.ac.in} ; ^{k_k_pandey3@rediffmail.com}
• 关键词：Dimethylgallyl ; Structure ; Bonding ; Cobalt ; Rhodium ; Iridium
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：1 July, 2012
• 卷：710
• 期：Complete
• 页码：6-11
• 文件大小：376 K

摘要

Electronic, molecular structures and bonding analysis of the terminal neutral dimethylgallyl complexes of cobalt, rhodium and iridium [Me(PMeub>3ub>)ub>2ub>(Meub>3ub>GaCl)M(GaMeub>2ub>)] (M聽=聽Co, Rh, Ir) and [Me(PMeub>3ub>)ub>2ub>ClIr(GaMeub>2ub>)] were investigated at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of聽dimethylgallyl iridium complex [Me(PMeub>3ub>)ub>2ub>(Meub>3ub>GaCl)M(GaMeub>2ub>)] is in excellent agreement with structurally characterized iridium complex. Mayer bond order of the optimized structures shows that the聽M-Ga聽bonds in these complexes are essentially M-Ga single bond, which is also supported by the performed energy decomposition analysis. The orbital interactions between the metal and gallium arise mainly from M聽鈫惵燝aMeub>2ub> 蟽 donation. In all complexes, the 蟺-bonding contribution is relatively smaller. The absolute values of the 螖Eub>Pauliub>, 螖Eub>intub> and 螖Eub>elstatub> contributions to the M-Ga bonds increase according to M聽=聽Co聽<聽Rh聽<聽Ir.