Synthesis and characterisation of binuclear and trinuclear organoimido complexes of tungsten-(VI) and -(V) and a binuclear tungsten(V) oxoanion. X-Ray crystal structures of [{WCl4(NEt)}2], [P(CH2Ph)Ph3][W3Cl7(NBut)3(µ-NPh)3], [P(CH2Ph)Ph3][W2Cl7(NR)2](R = Et or Ph), and [P(CH2Ph)Ph3][W2O2Cl7]
- 1 January 1990
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 1043-1051
- https://doi.org/10.1039/dt9900001043
Abstract
The X-ray crystal structure of [{WCl4(NEt)}2] has been determined and shows the molecule to be binuclear with asymmetric chlorine bridges and linear ethylimido groups having a W–N distance of 1.69(1)Å. Binuclear, mixed organoimido compounds [{WCl2(NBut)(µ-NR)(NH2But)}2](R = Ph or C6H4Me-p) with asymmetric NR bridges have been converted to the trinuclear anions [W3Cl7(NBut)3(µ-NR)3]–. The X-ray crystal structure of [W3Cl7(NBut)3(µ-NPh)3]– shows it to contain terminal, linear NBut groups with an average W–N distance of 1.70 Å, almost symmetrical bridging NPh groups with an average W–N distance of 2.00 Å, and a triply bridging chlorine. Carbon-13 and 1H n.m.r. spectra of this anion show that rotation of the phenyl rings in the µ-NPh groups is restricted. Reduction of [WXCl4] with 1 equivalent of sodium amalgam in the presence of chloride ions gave the distorted confacial bioctahedral tungsten(V) anions [W2X2Cl7]–(X = NEt, NPh, or O). X-Ray crystal structures of all three anions have been determined and show the π-bonding ligands to be terminal with average W–N distances of 1.69 (X = NEt) and 1.72 Å(X = NPh) and an average W–O distance of 1.67 Å. The W–W distances in the three anions are 2.839(4)(X = NEt), 2.835(4)(X = NPh), and 2.849(1)Å(X = O).Keywords
This publication has 31 references indexed in Scilit:
- Structure of di-μ-chloro-bis[trichloro(p-tolylimino)tungsten(VI)], [{WCl3(p-CH3C6H4N)}2(μ-Cl)2]Acta Crystallographica Section C Crystal Structure Communications, 1987
- Preparation and characterisation of mononuclear organoimido complexes of tungsten: X-ray crystal structures of [WCl4(NC6H4Me-p)(thf)], [P(CH2Ph)Ph3][WCl5(NC6H4Me-p)], and [WCl2(NPh)2(bipy)]J. Chem. Soc., Dalton Trans., 1987
- Studies of π-bonding perturbation in the tungsten-nitrogen multiple bond of isopropylimido tungsten(VI) complexes: The crystal and molecular structures of [W(NCHMe2)Cl4]2·C6H6 and [W(NCHMe2)Cl5][NEt4]Polyhedron, 1986
- Organo-imido alkoxides of tungsten(VI). The crystal and molecular structures of [W(NPh)(μ-OMe)(OMe)3]2 and [W(NPh)(OCMe3)3Cl(NH2CMe3)]Polyhedron, 1985
- Organoimido-complexes of tungsten-(VI)-(V), and -(IV) : crystal and molecular structures of [W(NPh)Cl3(PPh3)2] and [W(NPh)Cl2(PMe3)3]J. Chem. Soc., Dalton Trans., 1983
- Phenylimido complexes of tungsten(VI) and tungsten(V). The crystal and molecular structure of Trichloro(phenylimido)bis(trimethylphosphine)tungsten(V)Australian Journal of Chemistry, 1983
- Phenylimido tungsten(VI) alkoxidesPolyhedron, 1982
- Multiple metal-carbon bonds. 27. Preparation of tungsten(VI) phenylimido alkyl and alkylidene complexesJournal of the American Chemical Society, 1982
- A bisphenylnitrene complex of molybdenum with a bent nitrene ligand. Preparation and structure of cis-bis(phenylnitrene)bis(diethyldithiocarbamato)molybdenumJournal of the American Chemical Society, 1979
- The crystal structure of an oxidation product from the reaction between tungsten(V) chloride and trichloroacetonitrileJournal of the Chemical Society D: Chemical Communications, 1971