1,4-DICYANOBUTENE-BRIDGED BINUCLEAR RHODIUM(I) COMPLEXES AND THEIR CATALYTIC ACTIVITIES

Article abstract of DOI:10.1016/0022-328X(87)87015-8

Reactions of Rh(ClO4)(CO)(PPh3)2 with dicyano olefins, cis-NCCH=CHCH2CH2CN (c-DC1B), trans-NCCH=CHCH2CH2CN (t-DC1B), trans-NCCH2CH=CHCH2CN (t-DC2B), and NCCH2CH2CH2CN (DCB) produce the binuclear dicationic rhodium(I) complexes, <(CO)(PPh3)2RhNC-A-CNRh(PPh3)2(CO)>(ClO4)2 (NC-A-CN=c-DC1B (1), t-DC1B (2), t-DC2B (3), DCB (4)).Complexes 1 and 2 are catalytically active for the hydrogenation of c-DC1B and t-DC1B, respectively, to give DCB, while complex 3 catalyzes the isomerization of t-DC2B to give c-DC1B and t-DC1B, and the hydrogenation of t-DC2B to DCB at 100 deg C.