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B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway

Kumar, Rahul and Jagirdar, Balaji R (2013) B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway. In: INORGANIC CHEMISTRY, 52 (1). pp. 28-36.

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Official 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 center dot BH3, AB) and dimethylamine borane (Me2HN center dot BH3, DMAB). At room temperature, the reaction between RuCl(dppe)(2)]OTf] and AB or DMAB results in trans-RuH(eta(2)-H-2)(dppe)(2)]OTf] trans-RuCl(eta(2)-H-2)(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 eta(1)-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: Journal Article
Additional Information: Copyright for this article belongs to AMER CHEMICAL SOC, WASHINGTON
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Francis Jayakanth
Date Deposited: 18 Feb 2013 08:54
Last Modified: 18 Feb 2013 08:54
URI: http://eprints.iisc.ac.in/id/eprint/45768

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