The iron complex [FeH­(CO) (PNP)] (PNP = N­(CH2CH2PiPr2)2) is a highly active catalyst for ammonia borane dehydrocoupling at room temperature. Mainly linear polyaminoborane is obtained upon release of 1 equiv of H2. Mechanistic studies suggest that both hydrogen release and B–N coupling are metal-catalyzed and proceed via free aminoborane. Catalyst deactivation results from reaction with free BH3 that is formed by aminoborane rearrangement. Importantly, borane trapping with a simple amine allows for the observation of a TON that is unprecedented for a well-defined base metal catalyst.

Hydrogenolysis of the chlorosilanes and silyl triflates (triflate = trifluoromethanesulfonate, OTf -) Me3-nSiX1+n (X = Cl, OTf; n = 0, 1) to hydrosilanes at mild conditions (4 bar H2, room temperature) is reported using low loadings (1 mol-%) of the bifunctional catalyst [Ru(H)2CO(HPNP iPr )] (HPNP iPr = HN(CH2CH2P(iPr)2)2). Endergonic chlorosilane hydrogenolysis can be driven by chloride removal, e.g. with NaBAr F 4 (BAr F 4 -= B(C6H3-3,5-(CF3)2 -). Alternatively, conversion to silyl triflates enables facile hydrogenolysis with NEt3 as base, giving Me3SiH, Me2SiH2 and Me2SiHOTf, respectively, in high yields. An outer-sphere mechanism for silyl triflate hydrogenolysis is supported by DFT computations. These protocols provide key steps for the synthesis of the valuable hydrochlorosilane Me2SiClH, which can also be directly obtained in yields over 50% by hydrogenolysis of chlorosilane/silyl triflate mixtures. catalyzed hydrogenolysis of chlorosilanes and silyl triflates with low catalyst loadings.

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Terminal Ru IV nitride [RuN{N(CH 2 CH 2 PtBu 2 ) 2 }] (1) and [RuCl{N(CH 2 CH 2 PtBu 2 ) 2 }] (2a) form an equilibrium with bridging nitride [{(tBu 2 PCH 2 CH 2 ) 2 N}Ru(μ-N)RuCl{N(CH 2 CH 2 PtBu 2 ) 2 }] (3a). While 3a could only be spectroscopically characterized yet not isolated, the reaction of the divinylamido chloro complex