@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 {1476,
	title = {Synthesis and reactivity of side-on-bound dinitrogen metal complexes},
	journal = {Organometallics},
	volume = {25},
	number = {7},
	year = {2006},
	note = {ISI Document Delivery No.: 025SVTimes Cited: 59Cited Reference Count: 107},
	month = {Mar},
	pages = {1530-1543},
	type = {Review},
	abstract = {An up-to-date account of the Synthesis of side-on-bound dinitrogen complexes of the lanthanides, the actinides, and the transition elements over the past 40 years is given. In addition, the reactivity of these derivatives is summarized. There have been many complicated multinuclear Cluster complexes with the N-2 imbedded in a fashion that corresponds to side-on N-2. There have been some suggestions, as early as 1960. that side-on dinitrogen complexes should exist. However, a key date in this area is 1988, which is when the disamarium Complex (CP*Sm-2)(2)(mu-eta(2):eta(2)-N-2) was reported. It is this date that is used in this account as the real starting point for the area of side-on dinitrogen coordination chemistry. After 1988, side-on dinitrogen complexes are reviewed from the point of view of Synthesis, structure (N-N bond lengths, where applicable), and reactivity. What becomes apparent is that while there have been many new side-on dinitrogen complexes discovered recently, investigations into their reactivity patterns are still at a primitive stage.},
	keywords = {BRIDGING N-2 UNIT, COORDINATED DINITROGEN, DINUCLEAR TANTALUM COMPLEX, ELECTRONIC-STRUCTURE, END-ON, MOLECULAR NITROGEN, NICKEL-LITHIUM COMPLEX, RAY CRYSTAL-STRUCTURE, REDUCTION SYSTEM, X-RAY},
	isbn = {0276-7333},
	url = {<Go to ISI>://000236288100002},
	author = {MacLachlan, E. A. and Fryzuk,Michael D.}
}
@article {1251,
	title = {Addition of primary and secondary phosphines to dinuclear tantalum hydrides: Synthesis of phosphides and phosphinidenes via P-H bond activation},
	journal = {Organometallics},
	volume = {24},
	number = {7},
	year = {2005},
	note = {ISI Document Delivery No.: 909LJTimes Cited: 11Cited Reference Count: 42},
	month = {Mar},
	pages = {1419-1427},
	type = {Article},
	abstract = {The dinuclear complex ((RPh)[NPN]Ta)(2)(mu-H)(4) (where (RPh)[NPN] = [RP(CH2SiMe2NPh)(2)] and R = Ph, Cy) shows remarkable reactivity with molecular nitrogen, producing the side-on end-on bound dinitrogen complex ((RPh)[NPN]Ta)(2)(mu-eta(1):eta(2)-N-2)(mu-H)(2.) This tantalum tetrahydride also promotes other small molecule activation. Addition of secondary phosphines HPR{\textquoteright}(2) (R{\textquoteright} = Ph, Cy) to ((RPh)[NPN]Ta)(2)(mu-H)(4) accesses trihydride phosphide systems ((RPh)[NPN]Ta)(2)(mu-H)(3)(mu-PR{\textquoteright}(2)). Addition of primary phosphines H2PR" (R" = Cy, Ad) gives bridging phosphinidene tantalum complexes ((RPh)[NPN]Ta)(2)(mu-H)(2)(mu-PR"). Molecular structures as determined by X-ray crystallography for the complexes ((PhPh) [NPN]Ta)(2)(mu-H)(3)(mu-PCy2) and ((CyPh)[NPN]Ta)(2)(mu-H)(2)(mu 1-PAd) are presented. Isotopic labeling studies offer mechanistic insights into the reactivity of this tetrahydride system. Reaction Of Cy2PH with ((CyPh)[NPN]Ta)(2)(mu-D)(4), for instance, gives solely the monchydride dideuteride complex ((CyPh)[NPN]Ta)(2)(Y-H)(mu-D)(2)(mu-PCy2). This labeling study indicates that D-2 loss forms the reactive species, ((CyPh) [NPN]Ta)(2)(mu-D)(2), which promotes small molecule activation. Addition of CyPH2 to ((CyPh)[NPN]Ta)(2)(AtD)(4) gives a series of isotopomers, with an average composition of 0.67 H and 1.33 D, supporting a 1,2-H-2 elimination step to form the tantalum phosphinidenes. These results are tied into the general reactivity of ((RPh)[NPN]Ta)(2)(mu-H)(4).},
	keywords = {BRIDGING N-2 UNIT, CP-ASTERISK, DIAMIDOPHOSPHINE COMPLEXES, DINITROGEN LIGAND, EARLY TRANSITION-METALS, END-ON, IMIDE FORMATION, MOLECULAR-STRUCTURES, RAY CRYSTAL-STRUCTURE, SIDE-ON},
	isbn = {0276-7333},
	url = {<Go to ISI>://000227861100010},
	author = {Shaver, M. P. and Fryzuk,Michael D.}
}
@article {1252,
	title = {Cleavage of hydrazine and 1,1-dimethylhydrazine by dinuclear tantalum hydrides: Formation of imides, nitrides, and N,N-dimethylamine},
	journal = {Journal of the American Chemical Society},
	volume = {127},
	number = {2},
	year = {2005},
	note = {ISI Document Delivery No.: 887RZTimes Cited: 11Cited Reference Count: 21},
	month = {Jan},
	pages = {500-501},
	type = {Article},
	keywords = {BRIDGING N-2 UNIT, COORDINATION, DINITROGEN COMPLEX, END-ON, FUNCTIONALIZATION, LIGAND, METAL-COMPLEXES, N-N BOND, REDUCTIVE CLEAVAGE, SIDE-ON},
	isbn = {0002-7863},
	url = {<Go to ISI>://000226324500013},
	author = {Shaver, M. P. and Fryzuk,Michael D.}
}
@article {1250,
	title = {Phosphine-induced ancillary ligand orthometalation at a tantalum-tantalum double bond},
	journal = {Organometallics},
	volume = {24},
	number = {11},
	year = {2005},
	note = {ISI Document Delivery No.: 927XMTimes Cited: 0Cited Reference Count: 32},
	month = {May},
	pages = {2606-2611},
	type = {Article},
	abstract = {The dinuclear tantalum tetrahydride complexes ((RPh)[NPN]Ta)(2)(mu-H)(4) ([NPN] = (PhNSiMe2CH2)(2)PR; R = Ph, Cy) promote the asymmetric activation of molecular nitrogen to form ((RPh)[NPN]Ta)(2)(mu-eta(1):eta(2)-N-2)(mu-H)(2). The coordinatively unsaturated dinuclear dihydride, ((RPh)[NPN]Ta)(2)(mu-H)(2), has been proposed as the reactive intermediate, with a tantalum-tantalum double bond storing four electrons with which to reduce N-2. Efforts to trap ((CyPh)[NPN]Ta)(2)(mu-H)(2) with excess PMe3 at low temperatures promoted the formation of a green product, proposed to be (CyPh [NPN]Ta(PMe3))(2)(mu-H)(2). Attempts to isolate this product promoted the orthometalation of an ancillary ligand N-Ph ring, forming (CyPh)[NPN]Ta(mu-H)(2)[mu-N(C6H4)]Ta[PN](H)(PMe3). Addition of 1 equiv of PMe3 to ((PhPh)[NPN] Ta)(2)(mu-H)(4) immediately produced the analogous orthometalation derivative, [NPN]Ta(mu-H)(2)[mu-N(C6H4)]Ta[PN](H)(PMe3).},
	keywords = {BRIDGING N-2 UNIT, C-H ACTIVATION, CLEAVAGE, CRYSTAL-STRUCTURE, DINITROGEN LIGAND, DINUCLEAR, EARLY TRANSITION-METALS, END-ON, ORGANODIMETALLIC COMPLEXES, SIDE-ON},
	isbn = {0276-7333},
	url = {<Go to ISI>://000229233800011},
	author = {Shaver, M. P. and Fryzuk,Michael D.}
}
@article {933,
	title = {Dinitrogen coordination chemistry: On the biomimetic borderlands},
	journal = {Chemical Reviews},
	volume = {104},
	number = {2},
	year = {2004},
	note = {ISI Document Delivery No.: 773QMTimes Cited: 189Cited Reference Count: 177},
	month = {Feb},
	pages = {385-401},
	type = {Review},
	keywords = {BRIDGING N-2 UNIT, DIPORPHYRIN, ELECTRONIC-STRUCTURE, END-ON, IRON-MOLYBDENUM COFACTOR, NITROGENASE FEMO-COFACTOR, RAY CRYSTAL-STRUCTURES, REDUCTIVE CLEAVAGE, RUTHENIUM COFACIAL, TRANSITION-METAL-COMPLEXES, VANADIUM DIAMIDOAMINE COMPLEX},
	isbn = {0009-2665},
	url = {<Go to ISI>://000188934400003},
	author = {MacKay, B. A. 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 {734,
	title = {Vanadium and niobium diamidophosphine complexes and their reactivity},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {81},
	number = {12},
	year = {2003},
	note = {ISI Document Delivery No.: 751CNTimes Cited: 7Cited Reference Count: 27},
	month = {Dec},
	pages = {1431-1437},
	type = {Article},
	abstract = {The tridentate ligand precursors R{\textquoteright}P(CH2SiMe2NR")(2) ((R{\textquoteright}R{\textquoteright}{\textquoteright})[NPN]: R{\textquoteright} = Cy, Ph; R" = Ph, Mes, Me) were prepared from metathesis reactions of a lithiated amine, chloro(chloromethyl)dimethylsilane, the appropriate 1degrees phosphine, and n-butyl lithium and were isolated as solvent adducts. Metathesis between (CyPh)[NPN]Li-2(OEt2), 2, and VCl3(THF)(3) afforded ((CyPh)[NPN]VCl)(2), 7, whose solid-state structure was established by X-ray crystallography. Reduction attempts of the ((R{\textquoteright}R{\textquoteright}{\textquoteright})[NPN]VCl)(2) species with KC8 incorporated molecular nitrogen but were complicated by imide formation and ligand decomposition. Metathesis of 2 with NbCl2Me3 afforded the highly unstable complex (CyPh)[NPN]NbMe3, 15. Attempts to hydrogenate this species were unsuccessful.},
	keywords = {3-COORDINATE MOLYBDENUM(III), BRIDGING N-2 UNIT, COORDINATION, COORDINATION CHEMISTRY, DINITROGEN COMPLEX, END-ON, FUNCTIONALIZATION, HYDROGENATION, LIGAND, METATHESIS, NIOBIUM, REDUCTION, REDUCTIVE CLEAVAGE, SIDE-ON, TANTALUM COMPLEX, VANADIUM},
	isbn = {0008-4042},
	url = {<Go to ISI>://000187035400001},
	author = {Shaver, M. P. and Thomson, R. K. and Patrick, B. O. and Fryzuk,Michael D.}
}
@article {5078,
	title = {Synthesis, structure, and reactivity of diamidophosphine complexes of yttrium and the lanthanides},
	journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie},
	volume = {79},
	number = {7},
	year = {2001},
	note = {ISI Document Delivery No.: 473RETimes Cited: 10Cited Reference Count: 17},
	month = {Jul},
	pages = {1194-1200},
	type = {Article},
	abstract = {The reaction of the dilithiodiamidophosphine ligand precursor PhP(CH2SiMe2NPh)(2)Li-2(THF)(2)([NPN]Li-2(THF)(2)) with LnCl(3)(THF)(3) (Ln = Y, Sm, Ho. Yb. Lu; THF = tetrahydrofuran) in refluxing toluene generates the mononuclear complexes [NPN]LnCI(THF) in good yield. The molecular structures have been shown to be five-coordinate in the solid state and in solution. Attempts to prepare alkyl derivatives have only met with partial success; the reaction of MeMgCl with [NPN]YCl(THF) generates the partially characterized mixed-metal derivative [NPN]YMe2MgCl. The reaction with LiAlH4 results in complete ligand exchange and the formation of the tetranuclear lithium aluminum hydride derivative ([NPN]AlH2Li(THF))(2). Reduction of the lutetium derivative with KC8 and naphthalene generated the dinuclear naphthalene-bridged species {[NPN]Lu}(2)(mu-eta (4):eta (4)-C10H8) wherein each Lu centre engages in eta (4)-coordination to opposite sides of the arene moiety. X-ray crystallography was used to characterize the four complexes.},
	keywords = {aluminum, BRIDGING N-2 UNIT, CATALYSTS, CRYSTAL-STRUCTURE, DINITROGEN, F-BLOCK METALS, lanthanides, LIGAND, lithium, mixed-donor ligands, NAPHTHALENE, OLEFIN POLYMERIZATION, SIDE-ON, TERTIARY PHOSPHINE COMPLEXES, YTTRIUM},
	isbn = {0008-4042},
	url = {<Go to ISI>://000171061200016},
	author = {Fryzuk,Michael D. and Yu, P. H. 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.}
}
