B–H bond activation using an electrophilic metal complex: insights into the reaction pathway

Kumar, Rahul ; Jagirdar, Balaji R. (2013) B–H bond activation using an electrophilic metal complex: insights into the reaction pathway Inorganic Chemistry, 52 (1). pp. 28-36. ISSN 0020-1669

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic300390s

Related URL: http://dx.doi.org/10.1021/ic300390s

Abstract

A highly electrophilic ruthenium center in the [RuCl(dppe)2][OTf] complex brings about the activation of the B–H bond in ammonia borane (H3N·BH3, AB) and dimethylamine borane (Me2HN·BH3, DMAB). At room temperature, the reaction between [RuCl(dppe)2][OTf] and AB or DMAB results in trans-[RuH(η2-H2)(dppe)2][OTf], trans-[RuCl(η2-H2)(dppe)2][OTf], and trans-[RuH(Cl)(dppe)2], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B–H bond activation were obtained. In both cases, the reaction proceeds via an η1-B–H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:98610
Deposited On:21 Nov 2014 11:13
Last Modified:21 Nov 2014 11:13

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