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RESEARCH ARTICLE
Contents Vol 66(10)

Synthesis and Reactivity of Half-Sandwich Ruthenium κ2-Aminoborane Complexes

David A. Addy A , Joshua I. Bates A , Michael J. Kelly A , Joseph Abdalla A , Nicholas Phillips A , Ian M. Riddlestone A and Simon Aldridge A B
+ Author Affiliations
- Author Affiliations

A Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.

B Corresponding author. Email: Simon.Aldridge@chem.ox.ac.uk

Australian Journal of Chemistry 66(10) 1211-1218 https://doi.org/10.1071/CH13106
Submitted: 5 March 2013  Accepted: 27 May 2013   Published: 27 June 2013

Abstract

Cationic half-sandwich ruthenium complexes featuring κ2-bound aminoborane ligands can readily be accessed from 16-electron precursors via chloride abstraction in the presence of H2BNR2 (R = iPr, Cy). Complexes [Cp*Ru(L)(κ2-H2BNR2)][BArf4] (2a: R = iPr, L = PCy3; 2b: R = iPr, L = PPh3; 2c: R = iPr, L = 1,3-bis-(2,4,6-trimethylphenyl)-imidazol-2-ylidene; 3a: R = Cy, L = PCy3; Arf = C6H3(CF3)2‐3,5) were isolated in yields of ~60 %, and characterised in the solid state by X-ray crystallography (for 2a, 2c, and 3a). Low-field 11B NMR shifts for the coordinated aminoborane fragment, together with short Ru⋯B contacts (of the order of 1.97 Å) imply a relatively tightly bound borane ligand, a finding which is given further credence by the results of density functional theory studies (e.g. bond dissociation energies in the range 24 kcal mol–1; 1 kcal mol–1 = 4.186 kJ mol–1). In terms of reactivity, κ2 systems of this type, while potentially offering a versatile route to asymmetric κ1 systems, in fact undergo borane extrusion even in the presence of a single equivalent of added ligand.


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