Reactions between carbonylhydridotris(triphenylphosphine)iridium(I) and difluorophosphine oxide, sulphide, and selenide: identification of ionic intermediates
作者:E. A. V. Ebsworth、Philip G. Page、David W. H. Rankin
DOI:10.1039/dt9840002569
日期:——
Carbonylhydridotris(triphenylphosphine)iridium(I)(1) reacts with PF2HY (Y = O, S, or Se) at 190 K in CH2Cl2 to give [Ir(CO)H2(PPh3)3][PF2Y](2), identified by n.m.r. spectroscopy. When the solutions were allowed to warm above 220 K, PPh3 was liberated and complexes [Ir(CO)H2(PPh3)2(P′F2Y)] were formed [Y = Se, (3a); S, (3b); or O, (3c)]. Complexes (3a) and (3b) were initially produced in two isomeric
羰基氢化三(三苯基膦)铱(I)(1)在190 K的CH 2 Cl 2中与PF 2 HY(Y = O,S或Se )反应生成[Ir(CO)H 2(PPh 3)3 ] [ PF 2 Y](2),通过核磁共振光谱法鉴定。当溶液升温至220 K以上时,释放出PPh 3并形成配合物[Ir(CO)H 2(PPh 3)2(P'F 2 Y)] [Y = Se,(3a); [ M +(2)]。S,(3b);或O,(3c)]。配合物(3a)和(3b)最初以两种异构形式生成,其中PPh 3基团互为顺式或互为反式; 在室温下,顺式异构体缓慢异构化为反式异构体。对于复合物(3c)(Y = O),仅检测到反式异构体。在这些反应中形成了副产物[Ir(CO)H(PPh 3)2(P'F 3)],并报道了其nmr参数。关于(1)的反应中离子中间体的形成的含义,与通常被认为涉及(1)的PPh 3的初始损失的相关反应的机理进行了简要的考虑。