Synthesis and Dynamic Nuclear Magnetic Resonance Studies of Co-ordinatively Unsaturated Alkyne Complexes of Tungsten(II)

DOI: 10.1039/DT9880002071

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2071 - 2076 (1988)

Update date:2022-08-03

Topics: Synthesis Alkyne

Authors:

Carlton, Laurence

Davidson, Jack L.

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Article abstract of DOI:10.1039/DT9880002071

Complexes <CR')2>2> react with NaS2PMe2, NaS2CNMe2, or Tl(2-SC5H4N) to give monoalkyne CR')> (R = R'= Me, LL' = S2CNMe2 or 2-SC5H4N; R = Ph, R' = Me, LL' = S2CNMe2 or S2PMe2; R = R' = Ph, LL' = S2PMe2) or bis-alkyne derivatives CPh)2>.Dynamic n.m.r. studies of the monoalkyne complexes reveal fluxional behaviour due to propeller rotation of the co-ordinated alkyne (R = R' = Me, LL' = S2CNMe2 or 2-SC5H4N) whereas with R = Ph, R' = Me or Ph, LL' = S2PMe2 an alternative process attributed to dechelation of the chelate ligand is also observed.The S2PMe2 derivatives react with ligands L = CNBu^t, PMe2Ph, or P(OMe)3 to give 1:1 adducts CR)(L)> t, PMe2Ph, or P(OMe)3; R = Ph, L =PMe2Ph or P(OMe)3> some of which, L = P(OMe)3, dissociate in solution to give the equilibrium (i). 13C N.m.r. studies of CMe)> are CR)(L)><*>CR)> + L (i) interpreted in terms of a six-co-ordinate structure containing one monodentate and one bidentate S2PMe2 ligand, rather than a seven-co-ordinate bis-chelate structure.

Full text of DOI:10.1039/DT9880002071

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