Addition of H2C(3,5-Me2pz)2 (Bpm*) to [(η4-1,5-COD)Rh(acetone)2]BF4 affords the complex [Bpm*Rh(COD)]BF4, which is carbonylated under mild conditions into [Bpm*Rh(CO)2]BF4. One of the CO ligands can be easily displaced by PPh3, PMePh2, or P(OMe)3. The X-ray structures of [Bpm*Rh(CO)2]BF4 and [Bpm*Rh(CO)(PPh3)]BF4 have been determined and show a rhodium center in a square-planar environment. These complexes have been fully characterized by infrared and 1H, 13C, and 31P NMR spectroscopy. They are rather active precursors for the hydroformylation of oct-1-ene. They also promote the hydroaminomethylation reaction of terminal alkenes:  i.e., the direct production of alkylamines from successive hydroformylation, condensation of the resulting aldehydes with diethylamine, and hydrogenation of the enamines. (2-Methyloctyl)diethylamine and nonyldiethylamine are obtained from oct-1-ene/H2/CO/NHEt2 building blocks. The reaction rate can be significantly increased on addition of [RuH2(PPh3)4], which acts presumably as a hydride-donating species.

Dedicated to Professor Andre E. Merbach on the occasion of his 65th birthday, in recognition of his fundamental contribution to the coordination chemistry of the lanthanide and transition-metal ionsThe basic aqueous coordination chemistry of Ru II has been studied using the catalytically important TPPTS phosphine (TPPTS trisodium salt of 3,3',3''-phosphinetriylbenzenesulfonic acid) and small gas molecules (H 2 , CO, N 2 ) as ligands. As a result, new water-soluble ruthenium mixed hydride complexes, presumably key species in many industrial catalytic processes, have been formed and identified. The Ru II mixed hydrides were synthesized, and their formation was followed in situ by multinuclear NMR spectroscopy, pressurizing aqueous Ru II ÀTPPTS systems with H 2 and CO gas in sapphire NMR tubes. The formation equilibrium of these complexes is highly dependant on the temperature and the gas pressures. Under 50 atm of N 2 , the uniquecomplex has been identified, which could be the first step toward dinitrogen activation. Introduction. ± Interest in the chemistry