Synthesis and Oxidation Reactions of the Unsaturated Anion [Mn<sub>2</sub>(CO)<sub>6</sub>(<i>μ</i>-Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub>)]<sup>2</sup><sup>-</sup>
作者:Xiang-Yang Liu、Víctor Riera、Miguel A. Ruiz、Claudette Bois
DOI:10.1021/om0101590
日期:2001.7.1
the unsaturated dihydride [Mn2(μ-H)2(CO)6(μ-dppm)] (dppm = Ph2PCH2PPh2) with several reagents (Na−Hg, K, etc.) promotes dihydrogen elimination to yield the deep green anion [Mn2(CO)6(μ-dppm)]2-. Oxidation of the latter with [FeCp2]PF6 (Cp = η5-C5H5) gives the CO-bridged species [Mn2(μ-η1:η2-CO)(CO)6(μ-dppm)] or, if PR3 is present, the related complexes [Mn2(μ-η1:η2-CO)(CO)5(PR3)(μ-dppm)] (R = Ph, OMe)
用几种试剂(Na-Hg,K等)对不饱和二氢化物[Mn 2(μ- H)2(CO)6(μ- dppm)](dppm = Ph 2 PCH 2 PPh 2)进行化学还原可促进二氢消除,得到深绿色的阴离子[锰2(CO)6(μ -dppm)] 2 - 。后者的氧化,[FeCp 2 ] PF 6(CP = η 5 -C 5 H ^ 5)给出CO-桥接物种[锰2(μ - η1:η 2 -CO)(CO)6(μ -dppm)],或者,如果PR 3存在时,相关的配合物[锰2(μ - η 1:η 2 -CO)(CO)5(PR 3) (μ- dppm)](R = Ph,OMe)。在腈或1-炔烃的存在下阴离子的氧化得到腈或亚乙烯基桥连的衍生物〔锰2(μ - η 1:η 2 -L)(CO)6(μ -dppm)]以高产率(L = NCR或CCHR)。具有(μ - η 1:η 2在溶液-CO)配体显示动态行为和容易反应用CO,得到对应的[锰2(CO)7