Comparison of Structure and Reactivity of Phosphine-Amido and Hemilabile Phosphine-Amine Chelates of Rhodium
作者:Lindsay J. Hounjet、Robert McDonald、Michael J. Ferguson、Martin Cowie
DOI:10.1021/ic101883u
日期:2011.6.20
with oxygen to form the peroxo complex, [RhO2(P,P′-dppe)(P,N-Ph2PAr–)], and with iodomethane to yield [RhI(CH3)(P,P′-dppe)(P,N-Ph2PAr–)]. Hemilabile phosphine-amine compounds can also be prepared by reactions of [Rh(P,P′-dppe)(P,N-Ph2PAr–)] with Me3OBF4 or HBF4·Et2O, resulting in (thermodynamic) additions at nitrogen to form [Rh(P,P′-dppe)(P,N-Ph2PAr′)][BF4] or [Rh(P,P′-dppe)(P,N-Ph2PAr)][BF4], respectively
合成了一系列带有正膦基苯胺基和正膦基苯胺配体的单核和双核铑(I)配合物。质子单膦基苯胺Ph 2 PAr或PhPAr 2(Ar = o -C 6 H 4 NHMe)与0.5当量的[Rh(μ-OMe)(COD)] 2的反应导致形成中性酰胺基络合物, [Rh(COD)(P,N -Ph 2 PAr –)]或[Rh(COD)(P,N -PhP(Ar –)Ar)](Ar – = o -C 6H 4 NMe –)分别通过内部甲醇离子对胺进行化学计量控制的去质子化。类似地,双核配合物,铑[Rh 2(COD)2(μ- P,Ñ,P' ,N' -mapm 2- )](MAPM 2- =分析纯(AR -)PCH 2 P(氩- )中的Ar) ,可以通过质子二膦基苯胺,mapm(Ar 2 PCH 2 PAr 2)与1当量的[Rh(μ-OMe)(COD)] 2反应制备。可以通过monophosphinoanilines