Redox-dependent isomerization of organometallic RuII/Ru III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism

Seah Ling Kuan; Weng Kee Leong; Lai Yoong Goh; Richard D. Webster

doi:10.1021/om050432o

Redox-dependent isomerization of organometallic Ru^II/Ru ^III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism

Seah Ling Kuan
, Weng Kee Leong
, Lai Yoong Goh^*
, Richard D. Webster

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

28 Citations (Scopus)

Abstract

[Cp*Ru^III{HB(mt)₃}]X (1A(X); X = Cl, PF ₆) and [Cp*Ru^II{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*Ru^IIICl₂]₂ and [Cp*Ru^II(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*Ru^II{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.

Original language	English
Pages (from-to)	4639-4648
Number of pages	10
Journal	Organometallics
Volume	24
Issue number	19
DOIs	https://doi.org/10.1021/om050432o
Publication status	Published - 12 Sept 2005

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@article{b1681e31a8594906ab85081b767ac2c3,

title = "Redox-dependent isomerization of organometallic RuII/Ru III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism",

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.",

author = "Kuan, \{Seah Ling\} and Leong, \{Weng Kee\} and Goh, \{Lai Yoong\} and Webster, \{Richard D.\}",

year = "2005",

month = sep,

day = "12",

doi = "10.1021/om050432o",

language = "English",

volume = "24",

pages = "4639--4648",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "19",

}

TY - JOUR

T1 - Redox-dependent isomerization of organometallic RuII/Ru III compounds containing the hydrotris(methimazolyl)borate ligand

T2 - An electrochemical square scheme mechanism

AU - Kuan, Seah Ling

AU - Leong, Weng Kee

AU - Goh, Lai Yoong

AU - Webster, Richard D.

PY - 2005/9/12

Y1 - 2005/9/12

N2 - [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.

AB - [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.

UR - https://www.scopus.com/pages/publications/25444439864

U2 - 10.1021/om050432o

DO - 10.1021/om050432o

M3 - Article

SN - 0276-7333

VL - 24

SP - 4639

EP - 4648

JO - Organometallics

JF - Organometallics

IS - 19

ER -

Redox-dependent isomerization of organometallic Ru^II/Ru ^III compounds containing the hydrotris(methimazolyl)borate ligand: An electrochemical square scheme mechanism

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