Phosphorus-carbon bond cleavage at a di-iron centre: synthesis of μ-phosphidomethyl complexes [Fe2(CO)6(μ-CH2PR2)(μ-PR2)] from [Fe2(CO)6(μ-R2PCH2PR2)]
作者:Nancy M. Doherty、Graeme Hogarth、Selby A.R. Knox、Kirsty A. Macpherson、Frauke Melchior、David A.V. Morton、A.Guy Orpen
DOI:10.1016/s0020-1693(00)92368-5
日期:1992.8
which undergoes selective Me 2 PCH 2 bond cleavage to yield [Fe 2 (CO) 6 (μ-CH 2 PPh 2 )(μ-PMe 2 )], and of the bis-diphosphine complexes [Fe 2 (CO) 4 (μ-CO)(μ-R 2 PCH 2 PR 2 )(μ-Ph 2 PCH 2 PPh 2 )] (RPh, Me), which results only in Ph 2 PCH 2 bond cleavage to give [Fe 2 (CO) 4 (μ-R 2 PCH 2 PR 2 )(μ-CH 2 PPh 2 )(μ-PPh 2 )]. The ubiquity of μ-CH 2 PPh 2 is attributed to the existence of a zwitterionic
摘要在甲苯中加热回流时,二铁七羰基配合物[Fe 2(CO)6(μ-CO)(μ-R2 PCH 2 PR 2)](RPh,Me,Et,i Pr,OEt)失去一氧化碳,导致磷-亚甲基键断裂,得到μ-磷酰基甲基络合物[Fe 2(CO)6(μ-CH2 PR 2)(μ-PR2)]。在二膦配合物[Fe 2(CO)6(μ-CO)(μ-Ph2 PCH 2 PMe 2)]的热解中可以看到苯基稳定μ-CH 2 PR 2配体的能力。进行选择性的Me 2PCH2键裂解,生成[Fe 2(CO)6(μ-CH2 PPh 2)(μ-PMe2)],以及双-二膦配合物[Fe 2(CO)4( μ-CO)(μ-R2 PCH 2 PR 2)(μ-Ph2 PCH 2 PPh 2)](RPh,Me),仅导致Ph 2PCH2键断裂,得到[Fe 2 (CO)4(μ-R2 PCH 2 PR 2)(μ-CH2 PPh 2)(μ-PPh2)]。μ-CH2