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

Addy, D.A., Bates, J.I., Kelly, M.J., Abdalla, J., Phillips, N., Riddlestone, Ian M. and Aldridge, S. (2013) Synthesis and Reactivity of Half-Sandwich Ruthenium κ2-Aminoborane Complexes Australian Journal of Chemistry, 66 (10). pp. 1211-1218.

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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.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
Addy, D.A.
Bates, J.I.
Kelly, M.J.
Abdalla, J.
Phillips, N.
Riddlestone, Ian
Aldridge, S.
Date : 27 June 2013
DOI : 10.1071/CH13106
Depositing User : Clive Harris
Date Deposited : 24 Jun 2019 13:37
Last Modified : 24 Jun 2019 13:37

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