Reactivity of Rhenium(V) Oxo Schiff Base Complexes with Phosphine Ligands: Rearrangement and Reduction Reactions
作者:Paul D. Benny、Jenny L. Green、Hendrik P. Engelbrecht、Charles L. Barnes、Silvia S. Jurisson
DOI:10.1021/ic048670j
日期:2005.4.1
diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn)
对称rh(V)氧席夫碱配合物反式-[ReO(OH2)(acac2en)] Cl和反式-[ReOCl(acac2pn)],其中acac2en和acac2pn是四齿席夫碱配体N,N'-亚乙基双(乙酰丙酮)将二亚胺和N,N'-丙烯双(乙酰丙酮)二亚胺分别与单齿膦配体反应,生成两个独特的阳离子膦配合物之一,具体取决于配体骨架长度(en vs pn)和膦配体的身份。将Re(V)羰基还原为Re(III)是由于反式-[ReO(OH2)(acac2en)] Cl与三苯基膦或二乙基苯基膦反应而生成的一种单一的,还原的,通常类型为反式[Re]的二取代产物(III)(PR3)2(acac2en)] +。出乎意料的是,与更强的还原剂三乙基膦的类似反应导致分子内重排,不对称的顺式[[Re(V)O(PEt3)(acac2en)] +络合物。反式-[Re(V)O(acac2pn)Cl]与相同的膦配体反应只定量地重排了不