Intramolecular rearrangement behaviour of a dihydridoiridium (<scp>III</scp>)complex for med by regiospecific ‘chelate-assisted’ hydrosilylation
作者:Mary J. Auburn、Stephen R. Stobart
DOI:10.1039/c39840000281
日期:——
Addition of PPh2CH2CH2SiMe22H to [IrH(CO)](PPh3)3}is regiospecific as evidenced by formation of a cis adduct [I[graphic omitted]Me2)(CO)(PPh3)(H)(2H)]in which 2H nuclei are initially restricted to a single co-ordination position; subsequent rearrangement whereby 2H becomes equally distributed among the two hydridic sites is intramolecular with ΔG‡298= 19.3 ± 3.2kcal mol–1(1kcal = 4.184kJ).
PPh 2 CH 2 CH 2 SiMe 2 2 H加入[IrH(CO)](PPh 3)3 }具有区域特异性,这是通过形成顺式加合物[ I2](Me 2)(CO)(PPh 3)来证明的。)(H)(2 H)],其中2 H核最初被限制在单个配位位置;随后的重排使得2 H在两个氢化位点之间均等分布,这是分子内的,其ΔG ‡ 298 = 19.3±3.2kcal mol –1(1kcal = 4.184kJ)。