@article {2363,
	title = {Selective C-H Activation alpha to Primary Amines. Bridging Metallaaziridines for Catalytic, Intramolecular alpha-Alkylation},
	journal = {Journal of the American Chemical Society},
	volume = {131},
	number = {6},
	year = {2009},
	note = {ISI Document Delivery No.: 427PWTimes Cited: 22Cited Reference Count: 28Bexrud, Jason A. Eisenberger, Patrick Leitch, David C. Payne, Philippa R. Schafer, Laurel L.},
	month = {Feb},
	pages = {2116-+},
	type = {Article},
	abstract = {Selective alpha-C-H activation results in the synthesis of the first bridging metallaaziridine complex for the catalytic alpha-alkylation of primary amines. Reaction development led to the preparation of new Zr 2-pyridonate complexes for this useful transformation. No nitrogen protecting groups are required for this reaction, which is capable of assembling quaternary chiral centers a to nitrogen. Preliminary mechanistic investigations suggest bridging metallaaziridine species are the catalytically active intermediates for this alpha-functionalization reaction, while monomeric imido complexes furnish azepane hydroamination products.},
	keywords = {ALKENES, ALKYNES, BOND ACTIVATION, COMPLEXES, GENERATION, HYDROAMINOALKYLATION, INTERMOLECULAR HYDROAMINATION, NITROGEN, REACTIVITY, UNACTIVATED OLEFINS},
	isbn = {0002-7863},
	url = {<Go to ISI>://000264792200038},
	author = {Bexrud, J. A. and Eisenberger, P. and Leitch, D. C. and Payne, P. R. and Schafer, L. L.}
}
@article {1433,
	title = {Reaction of H2S with MoRu(CO)(6)(dppm)(2) to give H-2 and a bridged-sulfide product via hydrido-sulfhydryl intermediates (dppm = Ph2PCH2PPh2)},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {84},
	number = {2},
	year = {2006},
	note = {ISI Document Delivery No.: 040YKTimes Cited: 2Cited Reference Count: 29},
	month = {Feb},
	pages = {330-336},
	type = {Article},
	abstract = {Oxidative addition of H2S to MoRu(CO)(6)(mu-dppm)(2) (1) at similar to 20 degrees C in toluene yields an isolable complex formulated as Mo(CO)(3)(mu-SH)(mu-CO)(mu-dppm)(2)RuH(CO) (2) via the possible intermediate Mo(CO)(3)(mu-H)(mu-CO)(mu-dppm)(2)Ru(SH)(CO) (4) (dppm = Ph2PCH2PPh2) that is detectable at lower temperatures. Over 2 days, species 2 in toluene loses H-2 (and CO) to yield the bridged-sulfide product, Mo(CO)(2)(mu-CO)(mu-S)(mu-dppm)(2)Ru(CO) (5) that is also formed directly from the reaction of 1 with elemental sulfur. The solid-state molecular structure of 5 is determined by X-ray crystallography. A further hydrido-sulfhydryl species, possibly Mo(CO)(3)(mu-SH)(mu-H)(mu-dppm)(2)Ru(CO)(2) (3), is in equilibrium with 2 at ambient temperature.},
	keywords = {bis(diphenylphosphino) methane, bis(diphenylphosphino)methane, BOND ACTIVATION, bridged-sulfide complex, carbonyl complexes, CHEMISTRY, COMPLEXES, hydrido-sulfhydryl species, HYDROGEN, HYDROGEN-SULFIDE, MECHANISTIC ASPECTS, METAL, MO, MOLYBDENUM, RECOVERY, ruthenium, sulfide, SULFUR-DIOXIDE},
	isbn = {0008-4042},
	url = {<Go to ISI>://000237417600031},
	author = {Khorasani-Motlagh, M. and Safari, N. and Pamplin, C. B. and Patrick, B. O. and James, Brian R.}
}
@article {328,
	title = {C-H activation of substituted arenes by tungsten alkylidene complexes: Products, selectivity, and mechanism},
	journal = {Organometallics},
	volume = {21},
	number = {7},
	year = {2002},
	note = {ISI Document Delivery No.: 534QZTimes Cited: 18Cited Reference Count: 35},
	month = {Apr},
	pages = {1474-1486},
	type = {Article},
	abstract = {Thermolyses (70 degreesC, 40 h) of Cp*W(NO)(CH2CMe3)(2) (1) and Cp*W(NO)(CH2CMe3)(CH2C6H5) (2) in xylenes, mesitylene, and a,a,(x-trifluorotoluene generate mixtures of the corresponding aryl and/or benzyl products derived from aromatic sp(2) and benzylic sp(3) C-H bond activations of the solvent molecules by the intermediate alkylidene complexes Cp*W(NO)(=CHCMe3)(sigma-CMe4) (sigma-A) and Cp*W(NO)(=CHC6H5)(sigma-CMe4) (sigma-B), respectively. For instance, the thermolysis of 1 in p-xylene affords products resulting from the activation of one and two molecules of p-xylene. The two products derived from the activation of one solvent molecule are Cp*W(NO)(CH2CMe3)(C6H3-2,5-Me-2) (10) and CP*W(NO)(CH2CMe3)(CH2C6H4-4-Me)(2) (11). The other two complexes derived from the activation of two solvent molecules are Cp*W(NO)(CH2C6H4-4-Me)(C6H4-2,5-Me-2) (12) and Cp*W(NO)(CH2C6H4-4Me)(2) (13). The ratio of the four products in the final reaction mixture is 10:11:12:13 = 1.81 +/- 0.09:0.44 +/- 0.05:1.0:0.15 +/- 0.02. All new complexes prepared have been characterized as fully as possible by conventional spectroscopic methods, and the solid-state molecular structures of Cp*W(NO)(CH2C6H5)(C6H3-3,5-Me-2) (7) and Cp*W(NO)(CH2C6H5)(CH2C6H3-3,5-Me-2) (9) have been established by X-ray diffraction methods. Analyses of the product distributions resulting from the various thermolyses indicate that the benzyl products are increasingly favored over the aryl products as the number of methyl substituents on the solvent molecule increases. Likewise, the movement of the methyl groups from the ortho to meta to para position in the xylenes shifts the aryl vs benzyl product distribution toward the benzyl products. With respect to the aryl product regioselectivities, only the least sterically congested aryl regioisomers are formed in the activations of o- and m-xylene, while the meta and para aryl products are formed preferentially for (x,(x,(x-trifluorotoluene. Finally, the distributions obtained from sigma-B are more abundant in the aryl products than are those obtained from a-A. However, despite these general trends, it is also apparent that the origin of the observed product selectivities is highly dependent on the nature of the substrate, the nature of the C-H activation products, and the intermediate alkylidene complex.},
	keywords = {1, 2-RH-ELIMINATION, ARYL, BOND ACTIVATION, CARBON-HYDROGEN, FUNCTIONALIZATION, HYDROCARBON ACTIVATION, METHANE, MOLYBDENUM, ORGANOMETALLIC NITROSYL CHEMISTRY, REVERSIBLE, THERMOLYSIS},
	isbn = {0276-7333},
	url = {<Go to ISI>://000174599400020},
	author = {Adams, C. S. and Legzdins,Peter and Tran, E.}
}
@article {4995,
	title = {Intermolecular C-H activation of hydrocarbons by tungsten alkylidene complexes: An experimental and computational mechanistic study},
	journal = {Organometallics},
	volume = {20},
	number = {23},
	year = {2001},
	note = {ISI Document Delivery No.: 493VBTimes Cited: 17Cited Reference Count: 65},
	month = {Nov},
	pages = {4939-4955},
	type = {Article},
	abstract = {Cp*W(NO)(CH2CMe3)(2) (1) and Cp*W(NO)(CH2CMe3)(CH2C6H5) (2) under moderate conditions (70 degreesC, 40 h) generate the reactive complexes Cp*W(NO)(=CHCMe3) (A) and Cp*W(NO)(=CHC6H5) (B), respectively, which activate hydrocarbon solvents via the addition of C-H across the M=C bond. The alpha -deuterated derivative Cp*W(NO)(CD2CMe3)(2) (1-d(4)) undergoes intramolecular H/D exchange within the neopentyl ligands, consistent with the formation of a-neopentane complexes prior to neopentane elimination. The thermolysis of 1 in a 1:1 molar mixture of tetramethylsilane-h(12) and tetramethylsilane-d(12) (70 degreesC, 40 h) yields an intermolecular KIE of 1.07(4):1. Thermolysis of I and 2 in 1:1 benzene/benzene-d(6) yields intermolecular KIEs of 1.03(5):1 and 1.17(19):1, respectively. The KIE values are inconsistent with rate-determining C-H bond addition to the M=C linkage and indicate that coordination of the substrate to the metal center is the discriminating factor in alkane and arene intermolecular competitions. The complexes Cp*W(NO)(CH2CMe3)(C6D5) (5-d(5)) and CP*W(NO)(CH2C6H5)(C6D5) (6-d(5)) convert to the respective H/D scrambled products Cp*W(NO)(CHDsynCMe3)(C6D4H1) (5{\textquoteright}-d(5)) and Cp*W(NO)(CHDsynC6H5)(C6D4H1) (6{\textquoteright}-d(5)) under thermolytic conditions, consistent with the occurrence of reversible aromatic sp(2) C-H bond cleavage. The results suggest that the previously reported discrimination between the aryl and benzyl products of toluene activation by A and B originates from coordination of toluene to the metal center in two distinct modes. Supporting DFT calculations on the activation of toluene by CpW(NO)(=CH2) (C) indicate that aromatic sp(2) C-H bond activation proceeds through a pi -arene complex, while benzylic sp(3) C-H bond activation proceeds through a eta (2)(C,H),sigma -phenylmethane complex. The principal factor behind the preferential formation of the aryl products appears to be the relative energies of formation of these intermediates.},
	keywords = {BOND ACTIVATION, EFFECTIVE CORE POTENTIALS, EXCHANGE, METAL-ALKANE COMPLEXES, METHANE, METHYL-HYDRIDE, MOLECULAR CALCULATIONS, MOLYBDENUM, ORGANOMETALLIC NITROSYL CHEMISTRY, REDUCTIVE ELIMINATION},
	isbn = {0276-7333},
	url = {<Go to ISI>://000172243200026},
	author = {Adams, C. S. and Legzdins,Peter and McNeil, W. S.}
}
@article {4407,
	title = {Metal-based chirality and spin state change in 16-electron CpML2 systems: a computational study of CpW(NO)(PH3)},
	journal = {Chemical Communications},
	number = {17},
	year = {1998},
	note = {ISI Document Delivery No.: 116QXTimes Cited: 11Cited Reference Count: 35},
	month = {Sep},
	pages = {1903-1904},
	type = {Article},
	abstract = {Density functional theory calculations indicate that CpW(NO)(PH3) possesses a planar triplet ground state, a result with significant implications for the inversion of configuration of 16e, d(6) CpML2 species.},
	keywords = {alkane, ALKYL, BOND ACTIVATION, C-H ACTIVATION, EFFECTIVE CORE POTENTIALS, INTERMEDIATE, IRIDIUM(III) COMPLEXES, METHANE, MOLECULAR CALCULATIONS, REACTIVITY},
	isbn = {1359-7345},
	url = {<Go to ISI>://000075737000060},
	author = {Smith, K. M. and Poli, R. and Legzdins,Peter}
}
@article {7014,
	title = {PHOSPHINE COMPLEXES OF YTTRIUM, LANTHANUM, AND LUTETIUM - SYNTHESIS, THERMOLYSIS, AND FLUXIONAL BEHAVIOR OF THE HYDROCARBYL DERIVATIVES MR{\textquoteright}[N(SIME2CH2PME2)2]2 - X-RAY CRYSTAL-STRUCTURE OF Y[N(SIME2CHPME2)(SIME2CH2PME2)][N(SIME2CH2PME2)2]},
	journal = {Organometallics},
	volume = {10},
	number = {6},
	year = {1991},
	note = {ISI Document Delivery No.: FQ933Times Cited: 61Cited Reference Count: 41},
	month = {Jun},
	pages = {2026-2036},
	type = {Article},
	abstract = {{The preparation of phosphine complexes of the group 3 elements yttrium and lanthanum and the lanthanide metal lutetium is described. The reaction of 2 equiv of lithium salt of the mixed-donor ligand LiN(SiMe2CH2PR2)2 (R = Me, Ph, Pr(i)) with YCl3 or LuCl3 (R = Me only) leads to the formation of the bis(ligand) complexes MCl[N(SiMe2CH2PR2)2]2. The analogous lanthanum derivative requires the use of the corresponding potassium salt KN(SiMe2CH2PR2)2 (R = Me, Ph) with anhydrous LaCl3 to generate good yields of LaCl(N(SiMe2CH2PR2)2]2. Replacement of the remaining chloride with a hydrocarbyl ligand can be achieved for M = Y and Lu to generate MR[N(SiMe2CH2PMe2)2]2 (M = Y},
	keywords = {ALKYL, BOND ACTIVATION, CHEMISTRY, CRYSTALLOGRAPHIC CHARACTERIZATION, ELIMINATION, F-BLOCK METALS, HAFNIUM(IV), hydride, LIGAND, ORGANOLANTHANIDES},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1991FQ93300059},
	author = {Fryzuk,Michael D. and Haddad, T. S. and Rettig, S. J.}
}
