Facile Synthetic Access to Rhenium(II) Complexes: Activation of Carbon-Bromine Bonds by Single-Electron Transfer
作者:Yanfeng Jiang、Olivier Blacque、Thomas Fox、Christian M. Frech、Heinz Berke
DOI:10.1002/chem.200902600
日期:2010.2.15
the carbene ligand. For comparison, the dihydrogen ReI dibromide complexes [Re(Br)2(NO)(PR3)2(η2‐H2)] (R=Cy 2 a, iPr 2 b) were reacted with allyl‐ or benzylbromide, thereby affording the monophosphine ReII complex salts [R3PCH2R′][Re(Br)4(NO)(PR3)] (R′=CHCH2 6, Ph 7). The reduction of ReII complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford 1 a or 1 b in high yield
五个配位的Re I氢化物络合物[Re(Br)(H)(NO)(PR 3)2 ](R = Cy 1 a,i Pr 1 b)与苄基溴反应,得到17电子单核Re II氢化物络合物[Re(Br)2(H)(NO)(PR 3)2 ](R = Cy 3 a,i Pr 3b),其特征在于EPR,循环伏安法和磁化率测量。在二溴甲烷或溴仿的情况下,除Re之外,1的反应还生成Re II氢化物3我卡宾氢化物[回复(CHR 1)(BR)(H)(NO)(PR 3)2 ](R 1 = H 4,溴5 ; R =赛扬一个,我镨b),其中氢化物配位体是顺位定位于卡宾配体。为了比较,再二氢我二溴化物配合物[回复(BR)2(NO)(PR 3)2(η 2 -H 2)](R =赛扬2,我镨2 B)用烯丙基-苄基溴或反应,从而获得单膦ReII络合物盐[R 3 PCH 2 R'] [回复(BR)4(NO)(PR 3)](R'= CHCH