@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 {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 {537,
	title = {Parallel modes of C-H bond activation initiated by Cp*Mo(NO)(CH2CMe3)(C6H5) at ambient temperatures},
	journal = {Journal of the American Chemical Society},
	volume = {124},
	number = {33},
	year = {2002},
	note = {ISI Document Delivery No.: 584EVTimes Cited: 15Cited Reference Count: 32},
	month = {Aug},
	pages = {9680-9681},
	type = {Article},
	keywords = {ALKANES, ARYNE COMPLEXES, CHEMISTRY, HYDROCARBONS, INTERMEDIATE, METAL-COMPLEXES, MOLYBDENUM, REACTIVITY, THERMOLYSIS, TUNGSTEN ALKYLIDENE COMPLEXES},
	isbn = {0002-7863},
	url = {<Go to ISI>://000177455000012},
	author = {Wada, K. and Pamplin, C. B. and Legzdins,Peter}
}
@article {4543,
	title = {Mechanistic studies of the formation of zirconium alkylidene complexes [eta(5)-C5H3-1,3-(SiMe2CH2PPr2i)(2)]Zr=CHR(Cl) (R = Ph, SiMe3)},
	journal = {Journal of the American Chemical Society},
	volume = {121},
	number = {11},
	year = {1999},
	note = {ISI Document Delivery No.: 180AUTimes Cited: 33Cited Reference Count: 32},
	month = {Mar},
	pages = {2478-2487},
	type = {Article},
	abstract = {The reaction of [P2Cp]ZrCl3 (1) with 2 equiv of KCH2Ph generates an equilibrium mixture of alkyl complexes consisting of [P2Cp]ZrCl2(CH2Ph) (2), [P2Cp]ZrCl(CH2Ph)(2) (3), and [P2Cp]Zr(CH2Ph)(3) (4). Thermolysis of this mixture yields the alkylidene complex [P2Cp]Zr=CHPh(Cl) (5) in 85\% overall yield. Kinetic studies reveal a composite mechanism that incorporates the above preequilibrium, followed by an intramolecular alpha-abstraction reaction of dibenzyl 3 which follows a first-order rate, with the rate parameters Delta H double dagger = 19(1) kcal mol(-1) and Delta S double dagger = -22(5) cal(-1) mol K-1. A kinetic isotope effect of 3.0(5) was measured at 70 degrees C for the perdeuterated analogue [P2Cp]ZrCl(CD2C6D5)2. The reaction of 1 with 2 equiv of LiCH2-EMe3 (E = C, Si) produces a similar equilibrium mixture as observed for the benzyl analogues, consisting of [P2Cp]ZrCl2(CH2EMe3) (7), [P2Cp]Zr(CH2EMe3)(3) (8), and [P2Cp]ZrCl(CH2EMe3)(2) (9). Thermolysis of this mixture yields [P2Cp]Zr=CHEMe3(Cl) (6). A kinetic analysis conducted on 9 (E = Si) indicated a first-order reaction from which the activation parameters Delta H double dagger = 6(1) kcal mol(-1) and Delta S double dagger = -62(5) cal mol(-1) K-1 were obtained. The results indicate that reaction rates follow the order CH2Ph > CH2SiMe3 > CH2CMe3, an exact reversal of the trend for the homoleptic Ta systems Ta(CH2R)(5). The role of phosphine coordination is discussed to account for this trend. A crystal structure determination obtained for 6b reveals an alpha-agnostic interaction and a structure analogous to that of 5.},
	keywords = {ALPHA-HYDROGEN ABSTRACTION, CHEMISTRY, LIGAND, METAL-CARBON BONDS, NIOBIUM, OPENING METATHESIS POLYMERIZATION, tantalum, THERMOLYSIS, TITANIUM ALKYLIDENES, TITANOCENE},
	isbn = {0002-7863},
	url = {<Go to ISI>://000079363300019},
	author = {Fryzuk,Michael D. and Duval, P. B. and Mao, Sssh and Zaworotko, M. J. and Macgillivray, L. R.}
}
@article {3216,
	title = {MULTINUCLEAR COMPLEXES DERIVED FROM FERROCENYLPHOSPHINES AND TRIRUTHENIUM DODECACARBONYL},
	journal = {Organometallics},
	volume = {13},
	number = {9},
	year = {1994},
	note = {ISI Document Delivery No.: PF967Times Cited: 11Cited Reference Count: 37},
	month = {Sep},
	pages = {3594-3604},
	type = {Article},
	abstract = {{Pyrolysis of Ru-3(CO)(1)1(PFc(2)Ph) in hexanes for 15 h gave the trinuclear cluster Ru-3(CO)(8)(mu CO)(mu-H)[mu-eta(3)-(eta(5)-C(5)H(3)PFcPh)Fe(eta(5)-C5H5)] (11) in 20\% yield. Pyrolysis of Ru-3(CO)(12) with PFc(2)Ph in octane for 3.5 h gave the tetranuclear cluster RU(4)(CO)(11)(mu(3)-PFc)(mu-eta(1):eta(5)-C5H4) (12) in 12\% yield and the previously known 8, RU(4)(CO)(10)(mu-CO)mu(4)-PFc)(mu(4)-C6H4), in 10 yield: the mild conditions are noteworthy. Pyrolysis of Ru-3(CO)(12) With PEt(2)Fc in octane for 18 h gave the hexanuclear cluster complexes RU(6)C(CO)(14)(mu-PEt(2))(2) (13) and RU(6)C(CO)(13)(mu-PEt(2))(eta(5)-C5H5) (14) in 15\% and 25\% yields, respectively, and the pentanuclear derivative Ru-5(CO)(9)(mu-CO)(eta(6)-C6H6)(2)(mu(4)-PEt) (15) (low yield). Pyrolysis Of Ru-3(CO)(12) with PEtFc(2) in toluene for 10 h gave the pentanuclear cluster RU(5)(CO)(12)(mu(4)-PEt)(eta(6)-C7H8) (16) in similar to 5\% yield. Crystal data: 8, monoclinic, space group P2(1)/c},
	keywords = {benzene, MODE, MOLECULAR-STRUCTURES, OSMIUM CLUSTER, PH, phosphines, RAY CRYSTAL-STRUCTURE, RU3(CO)12, ruthenium, THERMOLYSIS},
	isbn = {0276-7333},
	url = {<Go to ISI>://A1994PF96700036},
	author = {Zheng, T. C. and Cullen, W. R. and Rettig, S. J.}
}
