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]
| Autor: | Richard L. Short, Michael B. Hursthouse, Donald C. Bradley, R. John Errington |
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| Rok vydání: | 1990 |
| Předmět: | |
| Zdroj: | J. Chem. Soc., Dalton Trans.. :1043-1051 |
| ISSN: | 1364-5447 0300-9246 |
| Popis: | 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)A. 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 A, almost symmetrical bridging NPh groups with an average W–N distance of 2.00 A, 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 A(X = NPh) and an average W–O distance of 1.67 A. The W–W distances in the three anions are 2.839(4)(X = NEt), 2.835(4)(X = NPh), and 2.849(1)A(X = O). |
| Databáze: | OpenAIRE |
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