@article {1263,
	title = {Synthesis and reactivity of zirconium and hafnium complexes incorporating chelating diamido-N-heterocyclic-carbene ligands},
	journal = {Journal of Organometallic Chemistry},
	volume = {690},
	number = {24-25},
	year = {2005},
	note = {ISI Document Delivery No.: 994VFTimes Cited: 36Cited Reference Count: 51},
	month = {Dec},
	pages = {5788-5803},
	type = {Article},
	abstract = {Early transition metal complexes employing a diamido N-heterocyclic carbene (NHC) ligand set (denoted [NCN]) render the centrally disposed NHC moiety stable to dissociation. Aminolysis reactions with the mesityl-substituted ligand precursor ((Mes)[NCN]H-2) and M(NMe2)(4) (M = Zr, Hf) provide bis(amido)-NHC-metal complexes that can be further converted to chloro and alkyl derivatives. Activation of (Mes)[NCN]M(CH3)(2) with [Ph3C][B(C6F5)(4)] yields {(Mes)[NCN]MCH3} {B(C6F5)(4)}, which is surprisingly inactive for the polymerization of 1-hexene. The zirconium cation did, however, show moderate ability to catalytically polymerize ethylene. The hafnium dialkyls are thermally stable with the exception of the diethyl complex, (Mes)[NCN]Hf(CH2CH3)(2), which undergoes P-hydrogen transfer and subsequent C-H bond activation with an ortho-methyl substituent on the mesityl group. The hafnium dialkyl complexes also insert carbon monoxide and substituted isocyanides to yield eta(2)-acyls and eta(2)-iminoacyls, respectively. In some circumstances, further C-C bond coupling occurs to yield enediolates and eneamidolate metallocycles. The molecular structures of (Mes)[NCN]Hf(CH2CHMe2)(2), (Mes)[NCN]Hf(eta(2)-(2,6-Me2C6H3NCCH3)(CH3), (Mes)[NCN]Hf(eta(2)-(2,6-Me2C6H3NCCH3)(2), (Mes)[NCN]Hf(OC(CH3)=C(CH3)NXy), and [(Mes)[NCN]Hf(OC(Bu-i)=C(Bu-i)O)](2) are included. (c) 2005 Elsevier B.V. All rights reserved.},
	keywords = {AMIDO, CARBON-MONOXIDE, CHEMISTRY, DONORS, ETA-2-IMINOACYL, hafnium, LIVING POLYMERIZATION, MIGRATORY INSERTION, N-heterocyclic carbene, OLEFIN, POLYMERIZATION, PROPERTIES, SPECTROSCOPIC, STABLE CARBENES, STRUCTURAL-CHARACTERIZATION, tridentate ligand, ZIRCONIUM, ZIRCONOCENE COMPLEXES},
	isbn = {0022-328X},
	url = {<Go to ISI>://000234058600046},
	author = {Spencer, L. P. and Fryzuk,Michael D.}
}
@article {392,
	title = {Synthesis, characterization, and solution redox properties of (trimpsi)M(CO)(2)(NO) complexes [M = V, Nb, Ta; trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)]},
	journal = {Inorganic Chemistry},
	volume = {41},
	number = {16},
	year = {2002},
	note = {ISI Document Delivery No.: 582RTTimes Cited: 7Cited Reference Count: 85},
	month = {Aug},
	pages = {4114-4126},
	type = {Article},
	abstract = {{Treatment of [Et4N][M(CO)(6)] (M = Nb, Ta) with I-2 in DME at -78 degreesC produces solutions of the bimetallic anions [M-2(mu-l)(3)(CO)(8)](-). Addition of the tripodal phosphine (BuSi)-Bu-t(CH2PMe2)(3) (trimpsi) followed by refluxing affords (trimpsi)M(CO)(3)I [M = Nb (1), Ta (2)], which are isolable in good yields as air-stable, orange-red microcrystalline solids. Reduction of these complexes with 2 equiv of Na/Hg, followed by treatment with Diazald in THF, results in the formation of (trimpsi)M(CO)(2)(NO) [M = Nb (3), Ta (4)] in high isolated yields. The congeneric vanadium complex, (trimpsi)V(CO)(2)(NO) (5), can be prepared by reacting [Et4N][V(CO)(6)] with [NO][BF4] in CH2Cl2 to form V(CO)(5)(NO). These solutions are treated with 1 equiv of trimpsi to obtain (eta(2)-trimpsi)V(CO)(3)(NO). Refluxing orange THF solutions of this material affords 5 in moderate yields. Reaction of (trimpsi)VCl3(THF) (6) with 4 equiv of sodium naphthalenide in THF in the presence of excess CO provides [Et4N][(trimpsi)V(CO)(3)] (7), (trimpsi)V(CO)(3)H, and [(trimpsi)V(mu-Cl)(3)V(trimpsi)][(eta(2)-trimpsi)V(CO)(4)].3THF ([8][9].3THF). All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 2.(1)/2THF, 3-5, and [8][9].3THF have been established by X-ray diffraction analyses. The solution redox properties of 3-5 have also been investigated by cyclic voltammetry. Cyclic voltammograms of 3 and 4 both exhibit an irreversible oxidation feature in CH2Cl2 (E-p},
	keywords = {CHARACTERIZATION, CHEMISTRY, DERIVATIVES, HIGHLY REDUCED ORGANOMETALLICS, ISOCYANIDE COMPLEXES, NITRIC-OXIDE, PHOSPHINE COMPLEXES, RAY CRYSTAL-STRUCTURES, SPECTROSCOPIC, tantalum, VANADIUM(II)},
	isbn = {0020-1669},
	url = {<Go to ISI>://000177365500013},
	author = {Hayton, T. W. and Daff, P. J. and Legzdins,Peter and Rettig, S. J. and Patrick, B. O.}
}
