From an <i>N</i>‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

Cabeza, Javier A.; Rı́o, Ignacio del; Miguel, Daniel; Sánchez-Vega, M. Gabriela

doi:10.1002/anie.200705154

Cited by 65 publications

(47 citation statements)

References 46 publications

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“…28 The X-ray structure of 23 ( Fig. 5) 28 shows that this hexanuclear complex arises from the condensation of two molecules of 19 and that it contains a quadruply-bridging carbyne fragment that arises from the activation of the third C-H bond of the original N-Me group. This structure is related to those of [Ru 6 (m 3 -H) 2 (m 5 -k 2 -ampy)(m-CO) 2 (CO) 14 ] (H 2 ampy = 2-amino-6-methylpyridine), which contains a quadruplybridging nitrene ligand, 29 and [Ru 6 (m 3 -H)(m 5 -k 2 -MebipyC)-(m-CO) 3 (CO) 13 ] (Me 2 bipy = 6,6 0 -dimethyl-2,2 0 -bipyridine), which contains a chelating Mebipy attached to a quadruplybridging carbyne fragment.…”

Section: Ruthenium Andmentioning

confidence: 99%

“…28 The NHC ligands of 45 and 47 arise from the cleavage of one C-N (45) or three C-H bonds (47) of the original Mes 2 Im ligand of compound 39. Using a 13 CO-enriched sample of compound 39, it has been determined that this carbide ligand arises from a thermallyinduced cleavage of CO, as had been previously observed for other carbide derivatives of osmium carbonyl.…”

Section: Ruthenium Andmentioning

confidence: 99%

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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%

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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“…La 4 Al 8 clusters and one La 5 Al 9 cluster produced multiple C À H bond activation featuring methylene, methine, or carbide C 1 functionalities. [16,17] The observation of methane and Me 3 AlA C H T U N G T R E N N U N G (PMe 3 ) in the NMR spectra, the irreversibility of the reaction, and the elemental analyses (Table 1) indicate that the few isolated crystals studied by X-ray diffraction must be similar in composition to the major product of the reaction.…”

Section: Reactivity Of [Lna C H T U N G T R E N N U N G (Alme 4 ) 3 ]mentioning

confidence: 99%

Elusive Trimethyllanthanum: Snapshots of Extensive Methyl Group Degradation in LaAl Heterobimetallic Complexes

Gerber

Roux

Törnroos

et al. 2008

Chemistry A European J

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Reactions of [La(AlMe4)3] and [Y(AlMe4)3] with PMe3 show that the phosphine can cleave Ln--CH3--Al linkages, separating Me3Al(PMe3). PMe3 (3 mol equiv) reacts with [Y(AlMe4)3] to give [(YMe3)n] contaminated with by-products containing phosphorus and aluminum. The La-based analog, [(LaMe3)n], is not formed selectively from the reaction of [La(AlMe4)3] with PMe3 or Et2O, which rather yields insoluble La/Al heterobimetallic products. Three multi-nuclear La-based clusters were obtained from a reaction of [La(AlMe4)3] with PMe3 (1 equiv) and identified by X-ray structure analyses. Each cluster exhibits extensive methyl group degradation and contains methylene, methine, or carbide moieties. [La4Al8(CH)4(CH2)2(CH3)20(PMe3)] has a [La4(CH)4] cuboid core supported by AlMe3, Me2AlCH2AlMe2, and PMe3 ligands. [La4Al8(C)(CH)2(CH2)2(CH3)22(toluene)] also contains a cuboid core, [La3Al(C)(CH)2(CH2)], which includes one exo cubic lanthanum atom, and is supported by AlMe3, Me3AlCH2AlMe2, (AlMe4)-, and toluene ligands. The lanthanum atoms in [La5Al9(CH)6(CH3)30] are arranged in a trigonal bipyramidal fashion with (CH) functionalities capping each face. The [La5(CH)6]3- core is formally balanced by three AlMe2 + moieties and is additionally supported by six AlMe3 ligands. The unit cell contains two independent La5 clusters, one with pseudo-C3h and the other with pseudo-D3 symmetry, as well as two molecules of the separation co-product Me3Al(PMe3).

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“…2 However, since the first study of the reaction of Ru 3 (CO) 12 with tetraaminealkenes (IEt 2 H 2 ) 2 to give complex Ru 3 (CO) 11 (IEt 2 H 2 ) reported by Lappert and Pye in 1977, 3 only a few reports dealing with Ru 3 (CO) 12 and NHCs ligands have been published. [4][5][6][7][8][9][10][11] Among these reactions, some abnormal intramolecular C-X (X = H, N) bond cleavage was observed. Cabeza et al demonstrated the synthesis of [Ru 3 (CO) 11 (Me 2 Im)] (Me 2 Im=1,3dimethylimidazol-2-ylidene) and its transformation into [Ru 3 (m-H) 2 (MeImCH)(CO) 9 ] through a process involving unusual reversible cleavage of two C-H bonds of a N-methyl group.…”

Section: Introductionmentioning

confidence: 99%

Reactions of indenyl-functionalized imidazolium salts and N-heterocyclic carbenes with Ru3(CO)12

et al. 2009

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Thermal treatment of indenyl-functionalized imidazolium salts and N-heterocyclic carbenes with Ru3(CO)12 gave different products. The normal mononuclear metal complexes (2a, 2b) were obtained via direct reaction of indenyl-functionalized imidazolium salts (1a, 1b) with Ru3(CO)12. Unexpected intramolecular C-H activated products (3a, 3b, 4a, 4b) were obtained via thermal treatment of corresponding indenyl-functionalized N-heterocyclic carbenes. All complexes were determined by 1H NMR, 13C NMR, IR spectra and elemental analysis. The molecular structures of 2b, 3a, 3b and 4b were determined by X-ray diffraction.

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From an N‐Methyl N‐Heterocyclic Carbene to Carbyne and Carbide Ligands via Multiple CH and CN Bond Activations

Cited by 65 publications

References 46 publications

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

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

Elusive Trimethyllanthanum: Snapshots of Extensive Methyl Group Degradation in LaAl Heterobimetallic Complexes

Reactions of indenyl-functionalized imidazolium salts and N-heterocyclic carbenes with Ru3(CO)12

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