Abnormal coordination of Arduengo's carbene upon reaction with M3(CO)12 (M = Ru, Os)

Crittall, Matthew R.; Ellul, Charles E.; Mahon, Mary F.; Saker, Olly; Whittlesey, Michael K.

doi:10.1039/b807923d

Cited by 68 publications

(50 citation statements)

References 26 publications

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“…The very bulky but also very basic NHCs 1,3-di-tertbutylimidazol-2-ylidene ( t Bu 2 Im) and 1,3-diadamantylimidazol-2-ylidene (Ad 2 Im) also reacts with one equivalent of [Ru 3 (CO) 12 ] at room temperature to give monosubstituted products (4 and 5 in Scheme 2), 17,18 but, in this case, the NHCs are abnormally coordinated 19 (through their C-4 atom) to the metal atom. It seems that the bulk of their N-R substituents prevents these carbenes from approaching the metal centre through the lone pair on the C-2 atom and that the stronger s-donating character of the abnormal NHCs (in comparison with that of the corresponding normal NHCs) 19,20 may also contribute to the driving force of these reactions.…”

Section: Ruthenium Andmentioning

confidence: 99%

The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters

Cabeza

García‐Álvarez

2011

Chem. Soc. Rev.

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In the last decade, chemists have dedicated many efforts to investigate the coordination chemistry of N-heterocyclic carbenes (NHCs). Although most of that research activity has been devoted to mononuclear complexes, transition-metal carbonyl clusters have not escaped from these investigations. This critical review, which is focussed on the reactivity of NHCs (or their precursors) with transition-metal carbonyl clusters (mostly are of ruthenium and osmium) and on the transformations underwent by the NHC-containing species initially formed in those reactions, shows that the polynuclear character of these metallic compounds or, more precisely, the close proximity of one or more metal atoms to that which is or can be attached to the NHC ligand, is responsible for reactivity patterns that have no parallel in the NHC chemistry of mononuclear complexes (74 references).

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Section: Ruthenium Andmentioning

confidence: 99%

The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters

Cabeza

García‐Álvarez

2011

Chem. Soc. Rev.

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“…31 In addition, examples with two d-block elements are those based on Pd-Pd, Zn-Zn, Ru-Ru, Ir-Ir and Au-Au systems. 21,[32][33][34][35][36][37] By contrast, no hetero-bimetallic NHDC complexes with two different d-block elements have been reported to date. Interestingly, hetero-bimetallic complexes, based on the related 1,2,4-triazolyl-3,5-diylidene carbenes, have been applied in tandem catalysis, and show superior performance compared to a combination of monometallic species due to cooperative effects.…”

mentioning

confidence: 99%

Ru–Ag and Ru–Au dicarbene complexes from an abnormal carbene ruthenium system

et al. 2015

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Reaction of [Ru(OAc)2(PPh3)2] with a P-functionalized imidazolium bromide easily affords a cationic abnormal carbene Ru system. Metalation with Ag2O yields a Ru-Ag complex containing an anionic dicarbene ligand, while subsequent transmetalation with Au(tht)Cl leads to the corresponding Ru-Au system. The bimetallic complexes were characterized by single crystal X-ray diffraction and are the first examples of complexes bearing anionic dicarbene ligands connecting two different d-block elements.

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“…When 21 was heated in THF to 50-70 • C, activation of the second backbone C H was observed resulting in the formation of the 3 -2 -bridging carbanionic carbene complex 22 containing a bridging hydride ligand. The Whittlesey group found a similar activation occurred between Arduengo's carbene, IAd, and Ru 3 (CO) 12 [84]. The equivalent reaction with Os 3 (CO) 12 with both IAd and I t Bu gave the abnormal carbene complex, the reaction required heating at 70 • C for 3 h due to the substitutionally inert Os CO bonds.…”

Section: Metal-mediated Activationmentioning

confidence: 82%