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DOI: 10.1039/A703725B (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 3225-3244

New ansa-2,2-bis(η-cyclopentadienyl)propane molybdenum and tungsten compounds and intramolecular hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride derivatives[hair space]

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Alexander Chernega, Jessica Cook, Malcolm L. H. Green, Luca Labella, Stephen J. Simpson, Joanne Souter and Adam H. H. Stephens

Abstract

The new compounds [Mo2Cl4(OEt)4(EtOH)2], [Mo{(η-C5H4)C(C5H10 )(η-C5H4)}Cl2], [W{(η-C5H4)CMe2(η-C 5H4)Cl2][BF4], [W{(η-C5H4)CMe2(η-C 5H4)}(SPh)2],* [W{(η-C5H4)CMe2(η-C 5H4)}(SPri)2], [W{(η-C5H4)CMe2(η-C 5H4)}(SPri)(NCMe)][BF4], [M{(η-C5H4)CMe2(η-C 5H4)}(NCMe)Cl][PF6] (M = Mo or W),* [W{(η-C5H4)CMe2(η-C 5H4)}(PPh3)Cl][PF6], [W{(η-C5H4)CMe2(η-C 5H4)}(CNC6H3Me2- 2,6)Cl][PF6],* [W{(η-C5H4)CMe2(η-C 5H4)}(η2-C2H4 )H][B(C6F5)4],* [W{(η-C5H4)CMe2(η-C 5H4)}Et(NCMe)][B(C6F5) 4], [W{(η-C5H4)CMe2(η-C 5H4)}Et(Cl)],* [W{(η-C5H4)CMe2(η-C 5H4)}Et(Cl)][BF4], [W{(η-C5H4)CMe2(η-C 5H4)}H3][PF6],* [M{(η-C5H4)CMe2(η-C 5H4)}Et2] (M = Mo or W),* [W{(η-C5H4)CMe2(η-C 5H4)}Et(I)], [W{(η-C5H4)CMe2(η-C 5H4)}Et(O2CPh)], [W{(η-C5H4)CMe2(η-C 5H4)}Et(X)] (X = H or D), [W{(η-C5H4)CMe2(η-C 5H4)}(CD3)2], [W{(η-C5H4)CMe2(η-C 5H4)}(CD3)I],* [W{(η-C5H4)CMe2(η-C 5H4)}(CD3)H] and [W{(η-C5H4)CMe2(η-C 5H4)}Me(D)] have been prepared. The asterisk indicates the crystal structure has been determined. Evidence is presented for intramolecular hydrogen–deuterium scrambling processes in the methyl- and ethyl-hydride compounds. Preliminary variable-temperature 1H NMR studies on [W{(η-C5H4)CMe2(η-C 5H4)}HA(HB)2] [PF6] give a value for J(AB) of 16 000 Hz at -70 °C.

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