@article {4052,
	title = {The versatility of lithium reagents in synthetic organometallic chemistry: Their differing reactions with [(CpMo)-Mo-*(NO)(CH2SiMe3)(2)]},
	journal = {Chemistry-a European Journal},
	volume = {3},
	number = {10},
	year = {1997},
	note = {ISI Document Delivery No.: YA856Times Cited: 13Cited Reference Count: 44},
	month = {Oct},
	pages = {1579-1587},
	type = {Article},
	abstract = {[Cp*Mo(NO)(CH2SiMe3)(2)] exhibits three principal types of reaction with the various lithium reagents investigated during this study, namely: regioselective deprotonation, reduction, and addition. Deprotonation of the reactant, achieved by treatment with lithium amide reagents, leads ultimately to the formation of the alkylidene {\textquoteright}{\textquoteright}ate{\textquoteright}{\textquoteright} complex [Cp*Mo(NO)(CH2SiMe3)(=CHSiMe3)](2)[Li-2(thf)(3)] (1). While LiN(SiMe3)(2) effects this conversion directly with no detectable intermediates, reaction with 1 equiv of LDA in THF for 15 min deprotonates the Cp* ligand to form the lithium salt of the {\textquoteright}{\textquoteright}tucked-in{\textquoteright}{\textquoteright} ate complex [(eta(5),eta(1)C(5)Me(4)CH(2))Mo(NO)(CH2SiMe3)(2)][Li(thf)(3)] (2) in 40\% isolated yield, Complex 2 slowly converts to the thermodynamically more stable 1 when left as a THF or C6D6 solution at ambient temperature fbr 48 h. Reaction of the dialkyl starting material with either tBuLi or PhLi leads to the production of the alkylidene complex 1 in irreproducible yields (10-50\% NMR; not isolable). A kinetic analysis of the reaction of [Cp*Mo(NO)(CH2SiMe3)(2)] with LiN(SiMe3)(2) indicated that the reaction was first-order in both the lithium and molybdenum reagents, and the activation parameters of Delta H-double dagger = 7,3 +/- 1.0 kcal mol(-1) and Delta S (double dagger) = -34 +/- 3 e.u. suggest an associative process. Treatment of the neutral dialkyl with 1 equiv of LiPPh2, in THF results in a one-electron reduction and production of {[Cp*Mo(NO)(CH2SiMe3)(2)][Li(thf)]}(2) (3). If left in solution, the 17e(-) dialkyl anion 3 is converted to the 18e(-) alkylidene anion 1 by the Ph2P-PPh2 coproduct, which effects the requisite hydrogen-atom abstraction. Finally, addition of a sterically undemanding alkyllithium reagent such as MeLi to the 16e(-) dialkyl reactant leads to the formation of the 18e(-) trialkyl anionic complex [Cp*Mo(NO)(CH2SiMe3)(2)(Me)][Li(thf)(3)] (4). Warming of 4 in a C6D6 solution results in loss of methane and production of 1. In most cases, the chemistry exhibited by the Mo system is duplicated by the analogous W congener, [Cp*W(NO)(CH2SiMe3)(2)]. The solid-state molecular structures of complexes 1 and 4 have been established by single-crystal X-ray crystallographic analyses.},
	keywords = {COMPLEXES, H BOND ACTIVATION, LIGAND, lithium, LIVING POLYMERIZATION, {ALKYLIDENE COMPLEXES},
	isbn = {0947-6539},
	url = {<Go to ISI>://A1997YA85600004},
	author = {Legzdins,Peter and Sayers, S. F.}
}
@article {3418,
	title = {ADDITION-REACTIONS OF CPMO(NO)(=CXCME(3)) (X=H, D) COMPLEXES WITH HETEROATOM-HYDROGEN BONDS},
	journal = {Organometallics},
	volume = {14},
	number = {1},
	year = {1995},
	note = {ISI Document Delivery No.: QB554Times Cited: 16Cited Reference Count: 37},
	month = {Jan},
	pages = {407-417},
	type = {Article},
	abstract = {{A mechanistic study of the thermal decomposition of CpMo(NO)(CD(2)CMe(3))(2) in solution provides clear evidence for the formation of CpMo(NO)(=CDCMe(3)). This transient 16-electron neopentylidene complex, either alpha-protio or alpha-deuterio, reads with the heteroatom-hydrogen bonds of amines and alcohols (EHR; R = alkyl, aryl; E = NH, O) to form neopentyl amide and alkoxide complexes of the general form CpMo(NO)(CH(2)CMe(3))(ER). The solid-state molecular structure of CpMo(NO)(CH(2)CMe(3))(NH-p-tolyl) (4) has been determined as a representative three-legged piano-stool molecule in this class. Crystals of 4 are monoclinic, space group P2(1)/c, with a = 11.243(2) Angstrom},
	keywords = {CARBENE COMPLEXES, CARBON BONDS, CRYSTAL-STRUCTURES, LOW-VALENT, {ALKYLIDENE COMPLEXES},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1995QB55400056},
	author = {Legzdins,Peter and Veltheer, J. E. and Young, M. A. and Batchelor, R. J. and Einstein, F. W. B.}
}
