@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 {615,
	title = {Activation and functionalization of molecular nitrogen by metal complexes},
	journal = {Chemical Record},
	volume = {3},
	number = {1},
	year = {2003},
	note = {ISI Document Delivery No.: 669WPTimes Cited: 48Cited Reference Count: 52},
	pages = {2-11},
	type = {Article},
	abstract = {Molecular nitrogen is intrinsically unreactive, so much so that it has confounded chemists for decades in attempts to functionalize this abundant diatomic molecule. While biological systems and industrial processes can fix nitrogen to form ammonia, the challenge is to discover a process that involves a homogeneous catalyst that can utilize N-2 as a feedstock to generate higher value organonitrogen materials. In this review, the activation of molecular nitrogen by transition metal complexes is reviewed with the view to present new kinds of transformations for coordinated dinitrogen. Moreover, some reaction types that are as yet unknown are outlined to try and stimulate further research in this area. (C) 2003 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.},
	keywords = {BRIDGING N-2 UNIT, CHEMISTRY, COORDINATED, COORDINATION CHEMISTRY, CRYSTAL-STRUCTURE, DINITROGEN, DINITROGEN COMPLEXES, END-ON, FIXATION, nitrogen fixation, nitrogenase, REDUCTION, SIDE-ON, transition metal complexes, ZIRCONIUM},
	isbn = {1527-8999},
	url = {<Go to ISI>://000182373700001},
	author = {Fryzuk,Michael D.}
}
@article {380,
	title = {Hydroboration of coordinated dinitrogen: A new reaction for the N-2 ligand that results in its functionalization and cleavage},
	journal = {Angewandte Chemie-International Edition},
	volume = {41},
	number = {19},
	year = {2002},
	note = {ISI Document Delivery No.: 604GZTimes Cited: 48Cited Reference Count: 30},
	pages = {3709-3712},
	type = {Article},
	keywords = {ACTIVATION, COMPLEX, DINITROGEN, END-ON, EXCHANGE, hydroboration, iron, MILD CONDITIONS, nitrides, NITROGEN, nitrogen fixation, REDUCTION, SIDE-ON, tantalum, TUNGSTEN},
	isbn = {1433-7851},
	url = {<Go to ISI>://000178609900046},
	author = {Fryzuk,Michael D. and MacKay, B. A. and Johnson, S. A. and Patrick, B. O.}
}
@article {4809,
	title = {The continuing story of dinitrogen activation},
	journal = {Coordination Chemistry Reviews},
	volume = {200},
	year = {2000},
	note = {ISI Document Delivery No.: 345HCTimes Cited: 235Cited Reference Count: 121},
	month = {May},
	pages = {379-409},
	type = {Review},
	abstract = {This review attempts to survey the recent literature concerning the coordination chemistry and the reactivity patterns of metal-dinitrogen complexes. In order that this work may stand alone, a certain amount of background information is included; however, the emphasis is on synthesis and reactivity patterns of recently discovered dinitrogen complexes. In addition, some effort is made to discuss new trends in dinitrogen chemistry as well as to point out underdeveloped topics in this area. (C) 2000 Elsevier Science S.A. All rights reserved.},
	keywords = {(1-PYRIDINIO)IMIDO, 3-COORDINATE MOLYBDENUM(III) COMPLEXES, BRIDGING N-2 UNIT, COMPLEXES, COORDINATED DINITROGEN, DINITROGEN, metal complexes, MOLECULAR, N BOND-CLEAVAGE, NITROGEN, nitrogen fixation, nitrogenase, RAY CRYSTAL-STRUCTURES, SIDE-ON, TO-END ROTATION, TRIAMIDOAMINE COMPLEXES},
	isbn = {0010-8545},
	url = {<Go to ISI>://000088809700013},
	author = {Fryzuk,Michael D. and Johnson, S. A.}
}
