Water soluble phosphine rhenium complexes

作者：Maccaroni Elisabetta; Dong Hailin; Blacque Olivier; Schmalle Helmut W; Frech Christian M; Berke Heinz^*

来源：Journal of Organometallic Chemistry, 2010, 695(4): 487-494.

DOI：10.1016/j.jorganchem.2009.11.031

• PTA
• Rhenium
• Transition metal hydrides
• Water solubility
• Olefin hydrogenation

Reduction of [NMe(4)](2)[ReBr(5)(NO)] (1) with zinc in acetonitrile leads to the known trisacetonitrile compound [ReBr(2)(CH(3)CN)(3)(NO)] (2). Attempts to turn 2 into a dihydrogen or a hydride complex applying direct reaction with H(2) or with H(2) and a base were unsuccessful. Complex 2 could be transformed into [ReBr(BF(4))mer(CH(3)CN)(3)(NO)] (2a) with AgBF(4) in acetonitrile and was used as a starting material in a ligand exchange reaction with the water soluble phosphine 1,3,5-triaza-7-phosphadamantane (PTA) to obtain the complex [ReBr(2)(NO)(PTA)(3)] (3). When the reduction of 1 with zinc was carried out in the presence of PTA in acetonitrile, the disubstituted complex [ReBr(2)(CH(3)CN)(NO)(PTA)(2)] (4) was formed. The olefin-coordinated rhenium complexes [ReBr(2)(NO)(CH(2)=CH(2))(PTA)(2)] (5a) and [ReBr(2)(NO)(PhCH=CH(2))(PTA)(2)] (5b) were obtained from the reaction of 4 with the corresponding olefins. Complex 4 reacts further with NaHBEt(3) in THF to give the dihydride [ReH(2)(THF)(NO)(PTA)(2)] (6). In the presence of ethylene 6 is transformed into the ethyl hydride complex [ReH(CH(2)CH(3))(eta(2)-C(2)H(4))(NO)(PTA)(2)] (7). Complexes 6 showed catalytic activity in the hydrogenation of olefins.

• 出版日期2010-2-15