@article {1573,
	title = {Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen},
	journal = {Proceedings of the National Academy of Sciences of the United States of America},
	volume = {103},
	number = {46},
	year = {2006},
	note = {ISI Document Delivery No.: 108OPTimes Cited: 14Cited Reference Count: 55Spencer, Liam P. MacKay, Bruce A. Patrick, Brian O. Fryzuk, Michael D.},
	month = {Nov},
	pages = {17094-17098},
	type = {Article},
	abstract = {Activation of molecular nitrogen by transition metal complexes is an area of current interest as investigations using the inert N-2 molecule to produce higher-value organonitrogen compounds intensify. In an attempt to extend the addition of hydride reagents E-H (where E = BR2, AIR(2), and SiR3) to the dinitrogen complex ([NPN]Ta)(2)(mu-H)(2)(mu-eta(2):eta(2)-N-2) [1; where NPN = (PhNSiMe2CH2)(2)PPh], the reaction with zirconocene chlorohydride, [Cp2Zr(Cl)H](x), was examined. The crystalline product formed in 35\% yield was determined to be ([NP(N)N]Ta)(mu-H)(2)(mu-N)(Ta[NPN])(ZrCP2) (2) in which the coordinated N-2 has been cleaved to form a phosphinimide bridging between Ta and Zr and a triply bridging nitride. The mechanism of this reaction was examined to determine the fate of the chloride and hydricle ligands attached to Zr in the starting zirconocene reagent. Using the zirconocene dihydride dimer ([Cp2ZrH2](2)), a higher yield of 2 was obtained (76\%), and H-2 was also observed by H-1 NMR spectroscopy. To probe the origin of the eliminated H-2, the dideuterated dinitrogen complex ([NPN]Ta)(2)(tLID)(2)(mu-eta(1):n(2)-N-2) (d(2)-1) was allowed to react with ([CP2ZrH2](2)), which resulted in the formation of ([NP(N)N]Ta)(mu-D)(2)(mu-N)(Ta[NPN]) (ZrCP2), (d(2)-2), with no evidence of hydrogen for deuterium scrambling between the starting zirconocene dihydride and the ditantalum dinitrogen complex. Studies into the use of preformed Zr(II) and Ti(II) reagents were also performed. The proposed mechanism involves initial adduct formation that facilitates inner-sphere electron transfer to cleave the N-N bond to form a species with bridging nitrides, one of which is transformed by nucleophilic attack of a phosphine donor to generate the observed phosphinimide.},
	keywords = {BOND-CLEAVAGE, BRIDGING N-2 UNIT, CLEAVAGE, COMPLEXES, dinitrogen coordination, END-ON, METAL-COMPLEXES, MOLECULAR, MOLYBDENUM-IRON PROTEIN, NITROGEN, nitrogen fixation, nitrogen-nitrogen bond, PHOSPHINIMIDE COMPLEXES, SIDE-ON, TANTALUM COMPLEX, TUNGSTEN},
	isbn = {0027-8424},
	url = {<Go to ISI>://000242249400008},
	author = {Spencer, L. P. and MacKay, B. A. and Patrick, B. O. and Fryzuk,Michael D.}
}
@article {1579,
	title = {N-N splitting of a functionalized mu-eta(1):eta(2) coordinated N-2 ligand leading to a mu-nitrido mu-imido core: mechanistic insight from DFT},
	journal = {Dalton Transactions},
	number = {9},
	year = {2006},
	note = {ISI Document Delivery No.: 021NKTimes Cited: 5Cited Reference Count: 35},
	pages = {1137-1140},
	type = {Article},
	abstract = {Silylation of a dinuclear tantalum complex containing a side- on end-on coordinated dinitrogen ligand initiates a sequence of reactions ultimately leading to a bis(mu-imido) structure. DFT is employed to determine the energetics of the entire reaction cascade. Particular emphasis is put on the unprecedented N-N cleavage reaction of the functionalized, mu-eta(1):eta(2) coordinated dinitrogen ligand. A mechanism for this reaction is derived theoretically and the corresponding transition state is determined.},
	keywords = {ammonia, ATOMS, BOND-CLEAVAGE, END-ON, MOLECULAR CALCULATIONS, POTENTIALS, REACTIVITY, SIDE-ON, SPECTROSCOPIC PROPERTIES, TANTALUM DINITROGEN COMPLEX},
	isbn = {1477-9226},
	url = {<Go to ISI>://000235989700003},
	author = {Studt, F. and MacKay, B. A. and Fryzuk,Michael D. and Tuczek, F.}
}
@article {4325,
	title = {Ligand elaboration mediated by a Cp*W(NO) template: Stepwise incorporation of small molecules into a tungsten vinyl fragment},
	journal = {Organometallics},
	volume = {17},
	number = {5},
	year = {1998},
	note = {ISI Document Delivery No.: ZC012Times Cited: 21Cited Reference Count: 81},
	month = {Mar},
	pages = {854-871},
	type = {Article},
	abstract = {{Thermolysis of the alkyl vinyl complex Cp*W(NO)(CH2SiMe3)(CPh=CH2) (1) in the presence of unsaturated, heteroatom-containing compounds such as esters and nitriles quantitatively affords metallacyclic products of reductive coupling. These are trapped as 18e complexes via either intramolecular rearrangement or intermolecular reaction with added trapping reagents. The nature of these metallacycles is consistent with the intermediacy of the acetylene complex Cp*W(NO)(eta(2)-CPh=CH) (A) derived in situ from the reductive elimination of SiMe4 from 1. With esters ROAc (R = Me, Et), reductive coupling and C-O bond cleavage yields the alkoxide-containing oxametallacyclopentadiene complexes Cp*W-(No)(eta(2)-O=C(Me)CH=CPh)(OR) (2},
	keywords = {ACTIVATION, ALKYNE COMPLEXES, BOND-CLEAVAGE, C-H, INSERTION, KETONE COMPLEXES, METAL-COMPLEXES, ORGANIC-SYNTHESIS, ORGANOMETALLIC NITROSYL CHEMISTRY, RAY CRYSTAL-STRUCTURE, SEQUENTIAL, ZIRCONOCENE COMPLEXES},
	isbn = {0276-7333},
	url = {<Go to ISI>://000072530700014},
	author = {Legzdins,Peter and Lumb, S. A. and Young, V. G.}
}
@article {7203,
	title = {IRON PORPHYRIN CATALYZED OXIDATION OF LIGNIN MODEL COMPOUNDS - THE OXIDATION OF VERATRYL ALCOHOL AND VERATRYL ACETATE},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {70},
	number = {8},
	year = {1992},
	note = {ISI Document Delivery No.: JW564Times Cited: 13Cited Reference Count: 43},
	month = {Aug},
	pages = {2314-2318},
	type = {Article},
	abstract = {meso-Tetra(2,6-dichloro-3-sulfonatophenyl)porphyrin iron chloride catalyzes the oxidation of 3,4-dimethoxybenzyl alcohol (veratryl alcohol) in aqueous solution to give veratraldehyde along with demethoxylation and ring-cleavage products. The isolation of a direct ring-cleavage product from the oxidation of veratryl acetate in aqueous solution supports the previously proposed ring-cleavage mechanisms. The oxidation in methanol, however, does not lead to ring-cleavage products. When veratryl alcohol was oxidized in methanol, solvent was found to be incorporated into the 3-position of veratryl alcohol, giving new insight into the mechanism of oxidation.},
	keywords = {3, 4-DIMETHOXYBENZYL ALCOHOL, BASIDIOMYCETE PHANEROCHAETE-CHRYSOSPORIUM, BOND-CLEAVAGE, C, CLEAVAGE, DEGRADING ENZYME, DIARYLPROPANE OXYGENASE, EXTRACELLULAR, HEME-ENZYME, LIGNINASES, RING, SPECTRAL CHARACTERIZATION, WHITE ROT BASIDIOMYCETE},
	isbn = {0008-4042},
	url = {<Go to ISI>://A1992JW56400025},
	author = {Cui, F. T. and Dolphin, D.}
}
