New ansa-2,2-bis(η-cyclopentadienyl)propane molybdenum and tungsten compounds and intramolecular hydrogen–deuterium exchange in methyl-hydride and ethyl-hydride derivatives
- 1 January 1997
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 18,p. 3225-3244
- https://doi.org/10.1039/a703725b
Abstract
The new compounds [Mo 2 Cl 4 (OEt) 4 (EtOH) 2 ], [Mo{(η-C 5 H 4 )C(C 5 H 10 )(η-C 5 H 4 )}Cl 2 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )Cl 2 ][BF 4 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(SPh) 2 ],* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(SPr i ) 2 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(SPr i )(NCMe)][BF 4 ], [M{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(NCMe)Cl][PF 6 ] (M = Mo or W),* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(PPh 3 )Cl][PF 6 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(CNC 6 H 3 Me 2 - 2,6)Cl][PF 6 ],* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(η 2 -C 2 H 4 )H][B(C 6 F 5 ) 4 ],* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(NCMe)][B(C 6 F 5 ) 4 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(Cl)],* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(Cl)][BF 4 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}H 3 ][PF 6 ],* [M{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et 2 ] (M = Mo or W),* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(I)], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(O 2 CPh)], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}Et(X)] (X = H or D), [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(CD 3 ) 2 ], [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(CD 3 )I],* [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}(CD 3 )H] and [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}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 1 H NMR studies on [W{(η-C 5 H 4 )CMe 2 (η-C 5 H 4 )}H A (H B ) 2 ] [PF 6 ] give a value for J(AB) of 16 000 Hz at -70 °C.Keywords
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