@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 {4143,
	title = {Thermal alkane C-H bond activation by a tungsten alkylidene complex: The reversal of alpha-hydrogen elimination},
	journal = {Journal of the American Chemical Society},
	volume = {119},
	number = {21},
	year = {1997},
	note = {ISI Document Delivery No.: XB674Times Cited: 52Cited Reference Count: 36},
	month = {May},
	pages = {5071-5072},
	type = {Article},
	keywords = {ABSTRACTION, ADDUCTS, ARYL, BINDING, CHEMISTRY, DERIVATIVES, LIGANDS, METAL-COMPLEXES, REACTIVITY, tantalum},
	isbn = {0002-7863},
	url = {<Go to ISI>://A1997XB67400046},
	author = {Tran, E. and Legzdins,Peter}
}
@article {3736,
	title = {Chloride metathesis or nitrosyl N-O bond cleavage in Cp(*)W(NO)(CH(2)SiMe(3))Cl upon treatment with alkali-metal alkoxides},
	journal = {Organometallics},
	volume = {15},
	number = {13},
	year = {1996},
	note = {ISI Document Delivery No.: UU281Times Cited: 13Cited Reference Count: 26},
	month = {Jun},
	pages = {2988-2993},
	type = {Article},
	abstract = {The bimetallic compound [Cp*W(NO)(CH(2)SiMe(3))](mu(2)-eta(1):eta(2)-NC{H}SiMe(3))[Cp*W(Cl)(O)]( 1), is produced in low yield by the heterogeneous reaction between Cp*W(NO)(CH(2)SiMe(3))Cl and KOCMe(3) in pentane. However, when this reaction is performed in THF or Et(2)O, the expected metathesis product, Cp*W(NO)(CH(2)SiMe(3))(OCMe(3)), is obtained. When Cp*W(NO)(CH(2)SiMe(3))Cl is treated with KOMe in pentane, a different bimetallic compound, [Cp*W(No)(CH(2)SiMe(3))Cl](mu-N)[Cp*W(Cl)(eta(2)-N{O}{H}CH(2)SiMe(3))] (2), is produced along with the known dioxo alkyl complex Cp*W(NO)(CH(2)SiMe(3)). Again, the expected alkyl alkoxide product, Cp*W(NO)(CH(2)SiMe(3))(OMe), is produced when the reaction is effected in THF or Et(2)O. The roles of KOCMe(3) or KOMe during the formation of complexes 1 and 2 are presently unclear. However, when the reactions are performed using the Li or Na alkoxide salts, the expected metathesis products, namely the alkyl alkoxide complexes, are indeed produced. The solid-state molecular structures of bimetallic complexes 1 and 2 have been established by single-crystal X-ray crystallographic analyses.},
	keywords = {ARYL, ASYMMETRIC COMPLEXES, CHEMISTRY, {ALKYL},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1996UU28100020},
	author = {Legzdins,Peter and Lundmark, P. J. and Rettig, S. J.}
}
@article {3306,
	title = {SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF [CP-ASTERISK-M(NO)(ETA(2)-CH(2)PH)(NCME)]BF4 SALTS (M=MO, W) AND RELATED COMPLEXES - THE STABILIZING INFLUENCE OF BENZYL LIGANDS},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {73},
	number = {7},
	year = {1995},
	note = {ISI Document Delivery No.: RT503Times Cited: 6Cited Reference Count: 29},
	month = {Jul},
	pages = {1035-1043},
	type = {Article},
	abstract = {Treatment of orange solutions of Cp*M(NO)(eta(2)-CH(2)Ph)Cl (M = Mo or W) with an equimolar amount of solid AgBF4 in MeCN affords the salts [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 as analytically pure crystals in good yields. Both orange complexes have been subjected to single-crystal X-ray crystallographic analyses in order to establish their molecular geometries and their intramolecular metrical parameters. Both salts consist of discrete organometallic cations and tetrahedral BF4- anions, the intramolecular dimensions of the two cationic complexes being essentially the same and resembling those found for related Cp*M(NO)-containing compounds. The isolated [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)](+) cations are quite electrophilic, being able to abstract Cl- from a NaCl IR cell to revert to their chloro precursors. However, treatment of the [Cp*W(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 salt with various unsaturated substrates (e.g., diphenylacetylene, 2,3-dimethyl-1,3-butadiene, carbon monoxide, and acetone) in CDCl3 results in no detectable chemical reaction. Lewis bases weaker than Cl- evidently cannot displace the acetonitrile ligand from the coordination sphere of the metal or induce the benzyl ligand to diminish its hapticity. Such a diminution does occur for the CH(2)Ph ligand when the MeCN group in the cationic complexes is replaced by a carboxylate anion to produce neutral Cp{\textquoteright}M(NO)(eta(1)-CH(2)Ph)(eta(2)-O(2)CR) complexes. The latter complexes are obtainable by treatment of Cp*M(NO)(eta(2)-CH(2)Ph)Cl with AgO(2)CR (R = CH(Et)(Ph)) in CH2Cl2 and have been fully characterized by conventional spectroscopic methods.},
	keywords = {ARYL, ASYMMETRIC COMPLEXES, BENZYL, CARBON-MONOXIDE, CATIONS, CP{\textquoteright}M(NO)R2, {ALKYL},
	isbn = {0008-4042},
	url = {<Go to ISI>://A1995RT50300017},
	author = {Dryden, N. H. and Legzdins,Peter and Sayers, S. F. and Trotter, J. and Yee, V. C.}
}
@article {3306,
	title = {SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF [CP-ASTERISK-M(NO)(ETA(2)-CH(2)PH)(NCME)]BF4 SALTS (M=MO, W) AND RELATED COMPLEXES - THE STABILIZING INFLUENCE OF BENZYL LIGANDS},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {73},
	number = {7},
	year = {1995},
	note = {ISI Document Delivery No.: RT503Times Cited: 6Cited Reference Count: 29},
	month = {Jul},
	pages = {1035-1043},
	type = {Article},
	abstract = {Treatment of orange solutions of Cp*M(NO)(eta(2)-CH(2)Ph)Cl (M = Mo or W) with an equimolar amount of solid AgBF4 in MeCN affords the salts [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 as analytically pure crystals in good yields. Both orange complexes have been subjected to single-crystal X-ray crystallographic analyses in order to establish their molecular geometries and their intramolecular metrical parameters. Both salts consist of discrete organometallic cations and tetrahedral BF4- anions, the intramolecular dimensions of the two cationic complexes being essentially the same and resembling those found for related Cp*M(NO)-containing compounds. The isolated [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)](+) cations are quite electrophilic, being able to abstract Cl- from a NaCl IR cell to revert to their chloro precursors. However, treatment of the [Cp*W(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 salt with various unsaturated substrates (e.g., diphenylacetylene, 2,3-dimethyl-1,3-butadiene, carbon monoxide, and acetone) in CDCl3 results in no detectable chemical reaction. Lewis bases weaker than Cl- evidently cannot displace the acetonitrile ligand from the coordination sphere of the metal or induce the benzyl ligand to diminish its hapticity. Such a diminution does occur for the CH(2)Ph ligand when the MeCN group in the cationic complexes is replaced by a carboxylate anion to produce neutral Cp{\textquoteright}M(NO)(eta(1)-CH(2)Ph)(eta(2)-O(2)CR) complexes. The latter complexes are obtainable by treatment of Cp*M(NO)(eta(2)-CH(2)Ph)Cl with AgO(2)CR (R = CH(Et)(Ph)) in CH2Cl2 and have been fully characterized by conventional spectroscopic methods.},
	keywords = {ARYL, ASYMMETRIC COMPLEXES, BENZYL, CARBON-MONOXIDE, CATIONS, CP{\textquoteright}M(NO)R2, {ALKYL},
	isbn = {0008-4042},
	url = {<Go to ISI>://A1995RT50300017},
	author = {Dryden, N. H. and Legzdins,Peter and Sayers, S. F. and Trotter, J. and Yee, V. C.}
}
