Complexes of molybdenum-(II) and -(IV) and tungsten(II) with sterically hindered thiolate ligands. Synthesis, reactivity, and X-ray crystal structures of [PPH4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] and [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]

Philip J. Blower, Jonathan R. Dilworth, John Hutchinson, Terry Nicholson, Jon A. Zubieta

Research output: Contribution to journalArticle

44 Scopus citations

Abstract

[MBr2(CO)4] (M = MO or W) react with thiolate anions SR- to give the anions [M(SR)3(CO)2]-(SR = SC6H2Pri3-2,4,6, SC6H3Pri2-2,6, SC6H2Br-4-Pri2-2,6, SC6H2Me3-2,4,6, SC6F5). The complex [PPh4][Mo(SC6H2Pri 3-2,4,6)3(CO)2] crystallises in space group P1 with a = 13.451 (2), b = 14.229(2), c = 19.862(3) Å, α = 96.11(1), β = 94.11(1), γ = 111.04(1)°, and Z = 2. Structure analysis based on 2 939 reflections with Io < 3.0σ(Io) refined to R = 0.0755. The anion has a trigonal-bipyramidal structure with axial co-ligands. The complexes [M(SR)3(CO)2]- react with CO to give [M(SR)3(CO)3]-. [Mo(SC6H2Pri3-2,4,6) 3(CO)2]- reacts with neutral donors L to give [Mo(SC6H2Pri3-2,4,6) 3(CO)L]- (L = MeCN, ButCN, PMe2Ph, or ButNC) and with [N2Ph][BF4] in MeCN to give [Mo(NNPh)(SC6H2Pri3-2,4,6) 3(NCMe)]. This complex crystallises in space group Pnma with a = 9.962(3), b = 21.002(4), c = 27.646(4) Å, and Z = 4. Structure analysis based on 1 772 reflections with Io > 3σ(Io) refined to R = 0.075. The NNPh and MeCN ligands occupy the axial sites of a trigonal bipyramid with the thiolates equatorial.

Original languageEnglish (US)
Pages (from-to)2639-2645
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number12
DOIs
StatePublished - Dec 1 1985
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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