Please use this identifier to cite or link to this item: https://doi.org/10.1021/om050432o
Title: Redox-dependent isomerization of organometallic RuII/Ru III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism
Authors: Kuan, S.L. 
Leong, W.K. 
Goh, L.Y. 
Webster, R.D.
Issue Date: 12-Sep-2005
Source: Kuan, S.L., Leong, W.K., Goh, L.Y., Webster, R.D. (2005-09-12). Redox-dependent isomerization of organometallic RuII/Ru III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism. Organometallics 24 (19) : 4639-4648. ScholarBank@NUS Repository. https://doi.org/10.1021/om050432o
Abstract: [Cp*RuIII{HB(mt)3}]X (1A(X); X = Cl, PF 6) and [Cp*RuII{HB(mt)3}] (2A) (Cp* = η5-C5-Me5, mt = N-methyl-2- mercaptoimidazol-1-yl) were synthesized by the reactions of K[HB(mt) 3] with [Cp*RuIIICl2]2 and [Cp*RuII(OMe)]2, respectively. 1A and 2A exist in the solid state in k3-S,S′,S″ coordination, so that the sulfur atom in each mt group coordinates to the central Ru ion, producing the normal tripodal geometry of the [HB(mt)3] ligand. However, both compounds undergo an isomerization reaction in solution, where the sulfur on one mt group is displaced in favor of coordination to the hydrogen bonded to the boron (an agostic B-H-Ru interaction), resulting in k3-H,S,S′ coordination about the Ru (K3-H,S,S′ forms of [Cp*Ru III{HB(mt)3}] and [Cp*RuII{HB(mt) 3}] are designated 1B and 2B, respectively). The rate and equilibrium constants associated with the reactions 1A ⇄ 2A ⇄ 2B ⇄ 1B ⇄ 1A have been determined by theoretical digital simulation comparisons of experimental 1H NMR spectroscopic and cyclic voltammetric data over a range of temperatures. © 2005 American Chemical Society.
Source Title: Organometallics
URI: http://scholarbank.nus.edu.sg/handle/10635/94698
ISSN: 02767333
DOI: 10.1021/om050432o
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