@article {1062, title = {Distinctive properties of Cp {\textquoteright} M(NO)(alkyl)(2) (M = MO, W) complexes}, journal = {Organometallics}, volume = {24}, number = {17}, year = {2005}, note = {ISI Document Delivery No.: 953ZRTimes Cited: 16Cited Reference Count: 40}, month = {Aug}, pages = {4088-4098}, type = {Review}, abstract = {This account summarizes our work with the title complexes, which are rare examples of electronically and coordinatively unsaturated transition-metal alkyls that can be isolated under ambient conditions. It first outlines the synthetic methods employed for the preparation of these compounds and then presents their distinctive physical properties. It then classifies the characteristic chemical properties of these complexes in terms of the reactivity being either metal or ligand based, and specific examples of particular transformations are illustrated with reference to the most studied systems.}, keywords = {CARBON BONDS, CP{\textquoteright}M(NO)R2, INTERMOLECULAR ACTIVATION, MIGRATORY INSERTION, MOLYBDENUM, NITRIC-OXIDE, ORGANOMETALLIC NITROSYL CHEMISTRY, {C-H BONDS}, isbn = {0276-7333}, url = {://000231124400002}, author = {Blackmore, I. J. and Jin, X. and Legzdins,Peter} } @article {879, title = {Reactivity of (trimpsi)V(NO)X-2 complexes (X = Cl, Br, I; trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)). Synthesis of the first group 5 alkyl nitrosyls}, journal = {Organometallics}, volume = {23}, number = {4}, year = {2004}, note = {ISI Document Delivery No.: 772ZFTimes Cited: 4Cited Reference Count: 40}, month = {Feb}, pages = {657-664}, type = {Article}, abstract = {Treatment of (trimpsi)V(NO)Cl-2 (trimpsi = (BuSi)-Bu-t(CH2PMe2)(3)) in NEt3 with 2 equiv each of p-toluic acid and Proton Sponge affords lemon yellow (trimpsi)V(NO)(eta(1)-O2C-4-C6H4Me)(2) (1) in 47\% isolated yield. Similarly, reaction of (trimpsi)V(NO)Cl-2 with 2 equiv of AgOTf in CH2Cl2 provides lemon yellow (trimpsi)V(NO)(OTf)(2) (2) in a comparable yield. Alternatively, 2 can be obtained directly in 40\% yield by treating CH2Cl2 solutions of (trimpsi)V(CO)(2)(NO) at -60 degreesC with 2 equiv of AgOTf. Likewise, both benzoyl peroxide and diphenyl disulfide are capable of oxidizing (trimpsi)V(CO)(2)(NO) under similar conditions to form (trimpsi)V(NO)X-2-type complexes, namely (trimpsi)V(NO)(O2CPh)(2) (3) and (trimpsi)V(NO)(SPh)(2) (4), respectively. The reactions of (trimpsi)V(NO)X-2 (X = Cl, Br) with Mg(CH2SiMe3)(2)(.)x(dioxane) (either 0.5 equiv or an excess) in THF afford the orange-red alkyl complexes (trimpsi)V(NO)(CH2SiMe3)X (X = Cl (5), Br (6)) in reasonable yields. Other members of this family of complexes such as (trimpsi)V(NO)(CH2CMe3)Cl (7) and (trimpsi)V(NO)(Me)Cl (8) can also be obtained by employing similar metathetical methodology, but all attempts to synthesize (trimpsi)V(NO)(alkyl)2 complexes have to date been unsuccessful. All new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1(.)1.5C(6)H(5)Me and 5(.)2C(4)H(8)O have been established by single-crystal X-ray diffraction analyses.}, keywords = {CHEMISTRY, CP{\textquoteright}M(NO)R2, CRYSTAL-STRUCTURES, DERIVATIVES, H BOND ACTIVATION, MOLYBDENUM, THERMAL-ACTIVATION, TUNGSTEN, V METAL-CARBONYLS, VANADIUM}, isbn = {0276-7333}, url = {://000188872700007}, author = {Hayton, T. W. and Patrick, B. O. and Legzdins,Peter} } @article {3306, title = {SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF [CP-ASTERISK-M(NO)(ETA(2)-CH(2)PH)(NCME)]BF4 SALTS (M=MO, W) AND RELATED COMPLEXES - THE STABILIZING INFLUENCE OF BENZYL LIGANDS}, journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie}, volume = {73}, number = {7}, year = {1995}, note = {ISI Document Delivery No.: RT503Times Cited: 6Cited Reference Count: 29}, month = {Jul}, pages = {1035-1043}, type = {Article}, abstract = {Treatment of orange solutions of Cp*M(NO)(eta(2)-CH(2)Ph)Cl (M = Mo or W) with an equimolar amount of solid AgBF4 in MeCN affords the salts [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 as analytically pure crystals in good yields. Both orange complexes have been subjected to single-crystal X-ray crystallographic analyses in order to establish their molecular geometries and their intramolecular metrical parameters. Both salts consist of discrete organometallic cations and tetrahedral BF4- anions, the intramolecular dimensions of the two cationic complexes being essentially the same and resembling those found for related Cp*M(NO)-containing compounds. The isolated [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)](+) cations are quite electrophilic, being able to abstract Cl- from a NaCl IR cell to revert to their chloro precursors. However, treatment of the [Cp*W(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 salt with various unsaturated substrates (e.g., diphenylacetylene, 2,3-dimethyl-1,3-butadiene, carbon monoxide, and acetone) in CDCl3 results in no detectable chemical reaction. Lewis bases weaker than Cl- evidently cannot displace the acetonitrile ligand from the coordination sphere of the metal or induce the benzyl ligand to diminish its hapticity. Such a diminution does occur for the CH(2)Ph ligand when the MeCN group in the cationic complexes is replaced by a carboxylate anion to produce neutral Cp{\textquoteright}M(NO)(eta(1)-CH(2)Ph)(eta(2)-O(2)CR) complexes. The latter complexes are obtainable by treatment of Cp*M(NO)(eta(2)-CH(2)Ph)Cl with AgO(2)CR (R = CH(Et)(Ph)) in CH2Cl2 and have been fully characterized by conventional spectroscopic methods.}, keywords = {ARYL, ASYMMETRIC COMPLEXES, BENZYL, CARBON-MONOXIDE, CATIONS, CP{\textquoteright}M(NO)R2, {ALKYL}, isbn = {0008-4042}, url = {://A1995RT50300017}, author = {Dryden, N. H. and Legzdins,Peter and Sayers, S. F. and Trotter, J. and Yee, V. C.} } @article {3306, title = {SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF [CP-ASTERISK-M(NO)(ETA(2)-CH(2)PH)(NCME)]BF4 SALTS (M=MO, W) AND RELATED COMPLEXES - THE STABILIZING INFLUENCE OF BENZYL LIGANDS}, journal = {Canadian Journal of Chemistry-Revue Canadienne De Chimie}, volume = {73}, number = {7}, year = {1995}, note = {ISI Document Delivery No.: RT503Times Cited: 6Cited Reference Count: 29}, month = {Jul}, pages = {1035-1043}, type = {Article}, abstract = {Treatment of orange solutions of Cp*M(NO)(eta(2)-CH(2)Ph)Cl (M = Mo or W) with an equimolar amount of solid AgBF4 in MeCN affords the salts [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 as analytically pure crystals in good yields. Both orange complexes have been subjected to single-crystal X-ray crystallographic analyses in order to establish their molecular geometries and their intramolecular metrical parameters. Both salts consist of discrete organometallic cations and tetrahedral BF4- anions, the intramolecular dimensions of the two cationic complexes being essentially the same and resembling those found for related Cp*M(NO)-containing compounds. The isolated [Cp*M(NO)(eta(2)-CH(2)Ph)(NCMe)](+) cations are quite electrophilic, being able to abstract Cl- from a NaCl IR cell to revert to their chloro precursors. However, treatment of the [Cp*W(NO)(eta(2)-CH(2)Ph)(NCMe)]BF4 salt with various unsaturated substrates (e.g., diphenylacetylene, 2,3-dimethyl-1,3-butadiene, carbon monoxide, and acetone) in CDCl3 results in no detectable chemical reaction. Lewis bases weaker than Cl- evidently cannot displace the acetonitrile ligand from the coordination sphere of the metal or induce the benzyl ligand to diminish its hapticity. Such a diminution does occur for the CH(2)Ph ligand when the MeCN group in the cationic complexes is replaced by a carboxylate anion to produce neutral Cp{\textquoteright}M(NO)(eta(1)-CH(2)Ph)(eta(2)-O(2)CR) complexes. The latter complexes are obtainable by treatment of Cp*M(NO)(eta(2)-CH(2)Ph)Cl with AgO(2)CR (R = CH(Et)(Ph)) in CH2Cl2 and have been fully characterized by conventional spectroscopic methods.}, keywords = {ARYL, ASYMMETRIC COMPLEXES, BENZYL, CARBON-MONOXIDE, CATIONS, CP{\textquoteright}M(NO)R2, {ALKYL}, isbn = {0008-4042}, url = {://A1995RT50300017}, author = {Dryden, N. H. and Legzdins,Peter and Sayers, S. F. and Trotter, J. and Yee, V. C.} } @article {2976, title = {FACILE NITROSYL N-O BOND-CLEAVAGE UPON THERMOLYSIS OF CP-ASTERISK-W(NO)PH2}, journal = {Organometallics}, volume = {13}, number = {5}, year = {1994}, note = {ISI Document Delivery No.: NL713Times Cited: 20Cited Reference Count: 18}, month = {May}, pages = {2088-2091}, type = {Note}, abstract = {{Thermolysis of Cp*W(NO)Ph2 (1) in C6H6 at 60-degrees-C for 24 h affords the new nitrosyl N-0 bond cleavage products Cp*W(eta2-ONPh)(NPh)Ph (2) and [Cp*W(O)Ph](mu-N)[Cp*W(NO)Ph] (3), as well as the known Cp*W(O)2Ph (4), in isolated yields of 10, 9, and 30\%, respectively. Complex 2 has been subjected to a single-crystal X-ray crystallographic analysis. Crystals of 2 are orthorhombic, space group Pcab, with a = 16.538(2) angstrom}, keywords = {CHEMISTRY, COMPLEXES, CP{\textquoteright}M(NO)R2, MOLYBDENUM, TUNGSTEN}, isbn = {0276-7333}, url = {://A1994NL71300077}, author = {Brouwer, E. B. and Legzdins,Peter and Rettig, S. J. and Ross, K. J.} }