@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 = {://000234058600046}, author = {Spencer, L. P. and Fryzuk,Michael D.} }