@article {706,
	title = {Thermal activation of hydrocarbon C-H bonds by Cp*M(NO) complexes of molybdenum and tungsten},
	journal = {Accounts of Chemical Research},
	volume = {36},
	number = {4},
	year = {2003},
	note = {ISI Document Delivery No.: 669GJTimes Cited: 54Cited Reference Count: 36},
	month = {Apr},
	pages = {223-233},
	type = {Review},
	abstract = {Gentle thermolysis of appropriate Cp*M(NO)(hydrocarbyl)(2) complexes (Cp* = eta(5)-C5Me5) of molybdenum and tungsten results in loss of hydrocarbon and the transient formation of 16-electron Cp*M(NO)-containing complexes such as Cp*M(NO)(alkylidene), Cp*M(NO)(eta(2)-benzyne), Cp*M(NO)(eta(2)-acetylene), and Cp*M(NO)(eta(2)-allene) (M = Mo, W). These intermediates effect the single, double, or triple activation of hydrocarbon C-H bonds intermolecularly, the first step of these activations being the reverse of the transformations by which they were generated. This Account summarizes the various types of C-H activations that have been effected with these nitrosyl complexes and also describes the results of kinetic, mechanistic, and theoretical investigations of these processes.},
	keywords = {ALKANES, ALKYLIDENE COMPLEXES, ARENES, CHEMISTRY, INTERMEDIATE, NITROSYL, REACTIVITY, REDUCTIVE ELIMINATION, THERMOLYSIS, TRANSITION-METAL BONDS},
	isbn = {0001-4842},
	url = {<Go to ISI>://000182343300001},
	author = {Pamplin, C. B. and Legzdins,Peter}
}
@article {5013,
	title = {alpha-agostic interactions in Cp*W(NO)(CH2CMe3)(2) and related nitrosyl complexes},
	journal = {Organometallics},
	volume = {20},
	number = {22},
	year = {2001},
	note = {ISI Document Delivery No.: 488TLTimes Cited: 22Cited Reference Count: 59},
	month = {Oct},
	pages = {4492-4501},
	type = {Article},
	abstract = {The solid-state molecular structure of Cp*W(NO)(CH2CMe3)(2) (1) has been shown to contain one "strongly agostic" and one "weakly agostic" methylene hydrogen atom by a neutron diffraction analysis at 120 K and by an X-ray diffraction analysis at -100 degreesC. The X-ray diffraction analysis of Cp*W(NO)(CH2SiMe3)(2) (2) at -20 degreesC reveals that its solid-state molecular structure possesses a crystallographically imposed mirror plane. Consequently, only the average existence of a relatively strong C-(HM)-M-... interaction for each hydrocarbyl ligand in 2 in the solid state can be established. The H-1 and gated C-13{H-1} NMR spectra of representative Cp{\textquoteright}M(NO)(R)(R{\textquoteright}) (M = Mo, W; R = hydrocarbyl, R{\textquoteright} = hydrocarbyl, halide, amide) complexes exhibit spectral parameters for the alpha -H and alpha -C atoms (i.e., delta (H), delta (C), Delta delta (H), DeltaJ(HC), and J(HW)) that provide evidence for the presence of a-agostic interactions in the molecular structures of these complexes in solution. The picture that has emerged from these investigations is that these complexes do adopt an a-agostic structure both in solution and in the solid state when secondary interactions such as pi -electron donation are weak (as in Cp*W(NO)(CH2CMe3)Cl), competitive (as in Cp*W(NO)(CH2CMe3)(CH2Ph)), or not possible (as in Cp*W(NO)(hydrocarbyl)(2) complexes generally). The bis(hydrocarbyl) complexes are probably stereochemically nonrigid in solution, as they appear to interconvert between the two limiting structures having one strongly agostic and one weakly agostic hydrocarbyl ligand. The neopentyl ligand forms alpha -agostic linkages with the metal centers in all neopentyl complexes studied, and these agostic interactions appear to be independent of the nature of the metal or the ancillary cyclopentadienyl ligand. Interestingly, the presence of these groundstate agostic interactions does not correlate with the tendency of the various compounds to undergo intramolecular alpha -H abstraction reactions and form reactive alkylidene complexes.},
	keywords = {ALKYL, C-H ACTIVATION, CARBON, COMPLEXES, CRYSTAL-STRUCTURE, DIALKYL COMPLEXES, hydride, HYDROGEN, MOLYBDENUM, TRANSITION-METAL BONDS, TUNGSTEN},
	isbn = {0276-7333},
	url = {<Go to ISI>://000171951700012},
	author = {Bau, R. and Mason, S. A. and Patrick, B. O. and Adams, C. S. and Sharp, W. B. and Legzdins,Peter}
}
