Facile synthetic access to rhenium(II) complexes: activation of carbon-bromine bonds by single-electron transfer

The five-coordinated Re(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (R=Cy 1 a, iPr 1 b) were reacted with benzylbromide, thereby affording the 17-electron mononuclear Re(II) hydride complexes [Re(Br)(2)(H)(NO)(PR(3))(2)] (R=Cy 3 a, iPr 3 b), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded Re(II) hydrides 3 in addition to Re(I) carbene hydrides [Re(=CHR(1))(Br)(H)(NO)(PR(3))(2)] (R(1)=H 4, Br 5; R=Cy a, iPr b) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re(I) dibromide complexes [Re(Br)(2)(NO)(PR(3))(2)(eta(2)-H(2))] (R=Cy 2 a, iPr 2 b) were reacted with allyl- or benzylbromide, thereby affording the monophosphine Re(II) complex salts [R(3)PCH(2)R'][Re(Br)(4)(NO)(PR(3))] (R'=-CH=CH(2) 6, Ph 7). The reduction of Re(II) 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. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3 a 150, 3 b 134 h(-1)) or allylbromide (TOF: 3 a 575, 3 b 562 h(-1)). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re(I) complexes [Re(Br)(2)(NO)(MeCN)(2)(PR(3))] (R=Cy 8 a, iPr 8 b), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h(-1)). Single-electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a, 6 a, 6 b, 7 a, 7 b, and 8 a were established by single-crystal X-ray diffraction studies.