π-Cyclopentadienyls of nickel(II) : VII. Carbon disulfide insertion reactions with thiolato-nickel compounds

doi:10.1016/S0022-328X(00)88919-6

Journal of Organometallic Chemistry

Volume 39, Issue 1, 1 June 1972, Pages 197-200

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Abstract

Mononuclear thiolatonickel compounds (I) and dinuclear thiolatonickel compounds (II) readily undergo carbon disulfide insertion, producing the stable (alkyl trithiocarbonato)nickel compounds (III) and (IV), respectively.

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η⁵-C₅H₅NiPBu₃CH(CN)₂ (I) readily undergoes ethyl- or phenyl-isothiocyanate insertion, producing the stable products η⁵-C₅H₅NiPBu₃SC(NRH) = C(CN)₂ (IIIa; R = C₂H₅, IIIb; R = C₆H₅. η⁵-C₅H₅NiPPh₃CH(CN)₂ (II) reacts with RNCS (R = C₂H₅ and C₆H₅) to undergo two types of insertion reaction; with C₂H₅NCS, η⁵C₅H₅NiPPh₃SC[N(C₂H₅)H] = C(CN)₂ (IVa) is obtained, with C₆H₅NCS, on the other hand, η⁵-C₅H₅NiPPh₃SC(NC₆H₅)CH(CN)₂ (IVb) is produced. p ]IIIa and IIIb react with PBu₃ to give ionic complexes [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₂H₅H)C(CN)₂]⁻ (Va) and [η⁵-C₅H₅Ni(PBu₃)₂]⁺ [SC(NC₆H₅)CH(CN)₂]⁻(Vb), respectively.
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Compounds of the type π-C₅H₅NiPBu₃SC(S)X (X = R, OR and NRH) are obtained from reactions between [π-C₅H₅Ni(PBu₃)₂]⁺Cl⁻ and SC(S)X⁻ in aqueous solution. Compounds such as π-C₅H₅NiPBu₃SC(S)NRH are also obtained by reactions of π-C₅H₅NiPBu₃SH with RNCS.
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π-Cyclopentadienyls of nickel(II) : VII. Carbon disulfide insertion reactions with thiolato-nickel compounds

Abstract

J. Organometal. Chem.

J. Organometal. Chem.

J. Organometal. Chem.