A. Choualeb, E. Maccaroni, O. Blacque
Jun 3, 2008
Citations
1
Influential Citations
34
Citations
Journal
Organometallics
Abstract
The tris(acetonitrile)dibromonitrosylrhenium(I) compound (1a) was obtained by reduction of the paramagnetic [NMe4]2[Re(NO)Br5] salt with Zn in MeCN. Subsequent reaction of 1a with THF produced the THF derivative [Re(NO)(THF)(MeCN)2Br2] (1b). Reaction of 1b with PiPr3, Pcy3, or P(p-tolyl)3 yielded bis(acetonitrile)-cis-dibromo(nitrosyl)-trans-bis(phosphine)rhenium complexes (R = iPr 2a, cy 2b, p-tolyl 2c). Treatment of 2a,b with excess NaBH4 produced the known borohydride complexes [Re(H)(η2-BH4)(NO)(PR3)2] (R = iPr 3a, cy 3b). Replacement of the BH3 moiety of 3a,b in THF by ethylene (1 bar) produced the dihydride complexes [Re(H)2(η2-C2H4)(NO)(PR3)2] (4) (R = iPr a, cy b). Protonation of 4a,b with HBF4·OEt2 afforded H2 and the monohydrido tetrafluoroborato species [Re(H)(NO)(PR3)2(η2-C2H4)(BF4)] (R = iPr 5a, cy 5b). X-ray diffraction studies were carried out on 1a, 2b,c, and 5b. Complexes 4a,b are catalytically active in olefin, imine, and ketone hydrogenations and in olefin and ketone hydrosilylations, a...