Abnormally bound N-heterocyclic carbene complexes of ruthenium: C-H activation of both C4 and C5 positions in the same ligand

Charles E Ellul; Mary F Mahon; Olly Saker; Michael K Whittlesey

Abnormally bound N-heterocyclic carbene complexes of ruthenium: C-H activation of both C4 and C5 positions in the same ligand

Charles E Ellul, Mary F Mahon, Olly Saker, Michael K Whittlesey

Department of Chemistry

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

123 Citations (SciVal)

Abstract

Abnormal carbene ligand formation from a free monodentate N-heterocyclic carbene, 1,3-di-tert-butyl-2-imidazolylidene occurs by coordination of the ruthenium centers to C4-position, rather than via C2-atom. Reaction of Ru3(CO)12 with free imidazolylidene 1,3-tBu2C3H2N2 gave [(1,3-tBu2C3H2N2-kC4)(CO)3Ru[Ru(CO)4]2] (1), having C2-position protonated, which undergoes thermal rearrangement and C5-H-activation at 50-70 Deg yielding [(micro -1,3-tBu2C3HN2-kC4:kC5)(micro -H)Ru3(CO)9] (2). Crystal structures of 1 and 2 are reported.

Original language	English
Pages (from-to)	6343-6345
Number of pages	3
Journal	Angewandte Chemie International Edition
Volume	46
Issue number	33
Publication status	Published - 2007

Keywords

imidazolylidenes
imidazolylidene hydro bridging ligand triruthenium nonacarbonyl cluster prepn structure
PREP (Preparation) (bridging
complexes
ruthenium complexes
Ligands Role
thermal rearrangement and C-H-bond activation of abnormally bound and bridging imidazolylidene triruthenium complexes)
Transition metal complexes Role
Molecular structure (of abnormally bound and bridging imidazolylidene triruthenium carbonyl complexes)
bond carbon hydrogen activation imidazolylidene ruthenium complex
ruthenium carbonyl cluster imidazolylidene abnormal activation metalation trinuclear complex
five-membered
Crystal structure
crystal structure ruthenium carbonyl cluster abnormal bound imidazolylidene
Metalation (prepn.
Carbonyl complexes Role
activation
mol structure ruthenium carbonyl cluster abnormal bound imidazolylidene
structure
RACT (Reactant or reagent) (ruthenium
RACT (Reactant or reagent) (carbene complexes
PRP (Properties)
RCT (Reactant)
PREP (Preparation)
prepn.
RACT (Reactant or reagent) (transition metal complexes
RACT (Reactant or reagent) (nitrogen
Heterocyclic compounds Role
Carbene complexes Role
ruthenium
Bond (carbon-hydrogen
SPN (Synthetic preparation)

APPLICATIONS OF N-HETEROCYCLIC CARBENE STABILISED RUTHENIUM HETEROATOM HYDRIDE COMPLEXES IN CATALYTIC & STOICHIOMETRIC T
Whittlesey, M. (PI)
Engineering and Physical Sciences Research Council
1/10/05 → 30/09/08
Project: Research council

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title = "Abnormally bound N-heterocyclic carbene complexes of ruthenium: C-H activation of both C4 and C5 positions in the same ligand",

abstract = "Abnormal carbene ligand formation from a free monodentate N-heterocyclic carbene, 1,3-di-tert-butyl-2-imidazolylidene occurs by coordination of the ruthenium centers to C4-position, rather than via C2-atom. Reaction of Ru3(CO)12 with free imidazolylidene 1,3-tBu2C3H2N2 gave [(1,3-tBu2C3H2N2-kC4)(CO)3Ru[Ru(CO)4]2] (1), having C2-position protonated, which undergoes thermal rearrangement and C5-H-activation at 50-70 Deg yielding [(micro -1,3-tBu2C3HN2-kC4:kC5)(micro -H)Ru3(CO)9] (2). Crystal structures of 1 and 2 are reported.",

keywords = "imidazolylidenes, imidazolylidene hydro bridging ligand triruthenium nonacarbonyl cluster prepn structure, PREP (Preparation) (bridging, complexes, ruthenium complexes, Ligands Role, thermal rearrangement and C-H-bond activation of abnormally bound and bridging imidazolylidene triruthenium complexes), Transition metal complexes Role, Molecular structure (of abnormally bound and bridging imidazolylidene triruthenium carbonyl complexes), bond carbon hydrogen activation imidazolylidene ruthenium complex, ruthenium carbonyl cluster imidazolylidene abnormal activation metalation trinuclear complex, five-membered, Crystal structure, crystal structure ruthenium carbonyl cluster abnormal bound imidazolylidene, Metalation (prepn., Carbonyl complexes Role, activation, mol structure ruthenium carbonyl cluster abnormal bound imidazolylidene, structure, RACT (Reactant or reagent) (ruthenium, RACT (Reactant or reagent) (carbene complexes, PRP (Properties), RCT (Reactant), PREP (Preparation), prepn., RACT (Reactant or reagent) (transition metal complexes, RACT (Reactant or reagent) (nitrogen, Heterocyclic compounds Role, Carbene complexes Role, ruthenium, Bond (carbon-hydrogen, SPN (Synthetic preparation)",

author = "Ellul, {Charles E} and Mahon, {Mary F} and Olly Saker and Whittlesey, {Michael K}",

year = "2007",

language = "English",

volume = "46",

pages = "6343--6345",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Inc.",

number = "33",

}

TY - JOUR

T1 - Abnormally bound N-heterocyclic carbene complexes of ruthenium: C-H activation of both C4 and C5 positions in the same ligand

AU - Ellul, Charles E

AU - Mahon, Mary F

AU - Saker, Olly

AU - Whittlesey, Michael K

PY - 2007

Y1 - 2007

N2 - Abnormal carbene ligand formation from a free monodentate N-heterocyclic carbene, 1,3-di-tert-butyl-2-imidazolylidene occurs by coordination of the ruthenium centers to C4-position, rather than via C2-atom. Reaction of Ru3(CO)12 with free imidazolylidene 1,3-tBu2C3H2N2 gave [(1,3-tBu2C3H2N2-kC4)(CO)3Ru[Ru(CO)4]2] (1), having C2-position protonated, which undergoes thermal rearrangement and C5-H-activation at 50-70 Deg yielding [(micro -1,3-tBu2C3HN2-kC4:kC5)(micro -H)Ru3(CO)9] (2). Crystal structures of 1 and 2 are reported.

AB - Abnormal carbene ligand formation from a free monodentate N-heterocyclic carbene, 1,3-di-tert-butyl-2-imidazolylidene occurs by coordination of the ruthenium centers to C4-position, rather than via C2-atom. Reaction of Ru3(CO)12 with free imidazolylidene 1,3-tBu2C3H2N2 gave [(1,3-tBu2C3H2N2-kC4)(CO)3Ru[Ru(CO)4]2] (1), having C2-position protonated, which undergoes thermal rearrangement and C5-H-activation at 50-70 Deg yielding [(micro -1,3-tBu2C3HN2-kC4:kC5)(micro -H)Ru3(CO)9] (2). Crystal structures of 1 and 2 are reported.

KW - imidazolylidenes

KW - imidazolylidene hydro bridging ligand triruthenium nonacarbonyl cluster prepn structure

KW - PREP (Preparation) (bridging

KW - complexes

KW - ruthenium complexes

KW - Ligands Role

KW - thermal rearrangement and C-H-bond activation of abnormally bound and bridging imidazolylidene triruthenium complexes)

KW - Transition metal complexes Role

KW - Molecular structure (of abnormally bound and bridging imidazolylidene triruthenium carbonyl complexes)

KW - bond carbon hydrogen activation imidazolylidene ruthenium complex

KW - ruthenium carbonyl cluster imidazolylidene abnormal activation metalation trinuclear complex

KW - five-membered

KW - Crystal structure

KW - crystal structure ruthenium carbonyl cluster abnormal bound imidazolylidene

KW - Metalation (prepn.

KW - Carbonyl complexes Role

KW - activation

KW - mol structure ruthenium carbonyl cluster abnormal bound imidazolylidene

KW - structure

KW - RACT (Reactant or reagent) (ruthenium

KW - RACT (Reactant or reagent) (carbene complexes

KW - PRP (Properties)

KW - RCT (Reactant)

KW - PREP (Preparation)

KW - prepn.

KW - RACT (Reactant or reagent) (transition metal complexes

KW - RACT (Reactant or reagent) (nitrogen

KW - Heterocyclic compounds Role

KW - Carbene complexes Role

KW - ruthenium

KW - Bond (carbon-hydrogen

KW - SPN (Synthetic preparation)

M3 - Article

SN - 1433-7851

VL - 46

SP - 6343

EP - 6345

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 33

ER -

Abnormally bound N-heterocyclic carbene complexes of ruthenium: C-H activation of both C4 and C5 positions in the same ligand

Abstract

Keywords

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APPLICATIONS OF N-HETEROCYCLIC CARBENE STABILISED RUTHENIUM HETEROATOM HYDRIDE COMPLEXES IN CATALYTIC & STOICHIOMETRIC T

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