Molybdenum, rhenium, and tungsten complexes with bi- and tri-dentate phosphinothiolato-ligands; structures of [Mo{PhP(CH2CH2S)2}2] and [Mo(NNMe2){PhP(CH2CH2S)2} 2]

Philip J. Blower, Jonathan R. Dilworth, G. Jeffery Leigh, Bryan D. Neaves, Fred B. Normanton, John Hutchinson, Jon A. Zubieta

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Abstract

[ReOCl3(PPh3)2] reacts with two equivalents of Ph2PCH2CH2SH in tetrahydrofuran to give [ReOCl(Ph2PCH2CH2S)2]. An excess of tridentate PhP(CH2CH2SH)2 reacts with [ReOCl3(PPh3)2] to yield [Re{PhP(CH2CH2S)2}{PhP(CH2CH 2S)(CH2CH2SH)}] containing a pendant unto-ordinated SH group. This complex reacts reversibly with CO to form [Re{PhP(CH2CH2S}{PhP(CH2-CH2S) (CH2CH2SH)}(CO)] [ν(CO) at 1 980 Cm-1]. The MIV complexes [MCl4L2] [M = MO or W, L = PPh3 or MeCN) react with PhP(CH2CH2SH)2 in MeOH to give [M{PhP(CH2CH2S)2}2]. An X-ray crystal-structure determination for the complex with M = Mo showed a distorted octahedral structure with an average MO-S distance of 2.44 Å. The complex crystallises in the triclinic space group P1, with a = 10.601(7), b = 10.867(4), c = 12.347(1) Å, α = 66.98(3), β = 85.60(4), γ = 63.70(4)°, and Z = 2. 1 337 Unique reflections with Io ≥ 3σ(Io) used in the solution converged at R = 0.0979. The hydrazido(2-) complexes [MCl(NNMe2)2(PPh2)2]Cl react with PhP(CH2CH2SH)2 in MeOH to give [M(NNMe2){PhP(CH2CH2S)2} 2] (M = Mo or W). An X-ray crystal-structure determination of the complex with M = Mo revealed a distorted pentagonal-bipyramidal structure with a linear apical NNMe2 ligand. The complex crystallises in the monoclinic space group P21/n, with a = 11.349(2), b = 12.403(3), c = 19.302(4) Å, β = 104.28(2)°, and Z = 4. 2 796 Unique reflections with Io > 3σ(Io) used in the solution converged at R = 0.605.

Original languageEnglish (US)
Pages (from-to)2647-2653
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number12
DOIs
StatePublished - 1985
Externally publishedYes

ASJC Scopus subject areas

  • General Chemistry

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