Five-co-ordinate nitrosyl thiolato-complexes of molybdenum and tungsten. the preparation and X-ray crystal structures of [nHEt3][Mo(SPh)4(NO)],[PPh4][WCl(SPh) 3(NO)], and [mo(SC6H2Pri3-2,4,6) 3(NH3)(NO)]

Peter T. Bishop, Jonathan R. Dilworth, John Hutchinson, Jon Zubieta

Research output: Contribution to journalArticle

22 Scopus citations

Abstract

Reaction of either [MCl3(PPh3)2(NO)] (M = Mo or W) or '{Mo(NH2O)(H2O)x(NO)}n' with -SR (R = Ph, C6H4Me-4, C6H4Cl-4, C6H2Me3-2,4,6, or But) in methanol gives the anionic five co-ordinate complexes [M(SR)4(NO)]- (M = Mo; R = Ph, C6H4Me-4, C6H4Cl-4, or C6H2Me3-2,4,6), [MCl(SR)3(NO)]- (M = Mo, R = But; M = W, R = Ph). Crystal data: for [NHEt3][Mo(SPh)4-(NO)], space group P21/n with a = 10.996(2), b = 16.127(4), c = 18.845(4) Å, α = 90.00, β = 105.94(1), γ = 90.00°, and Z = 4; 2 786 reflections used in structure solution, giving R = 0.0516; for [PPh4][WCl(SPh)3(NO)], space group P21/c, a = 10.809(1), b = 19.677(3),c = 19.250(3) Å, α = 90.00, β = 105.85(1), γ = 90.00°, and Z = 4; 1 895 reflections giving R = 0.0375. Both anions have overall trigonal-bipyramidal geometries with apical NO groups. The reaction of the polymeric species '{Mo(NH2O)(H2O)x(NO)}n' with the sterically hindered thiol 2,4,6-tri-isopropylthiophenol in refluxing methanol affords the ammine complex [Mo(SC6H2Pri3-2,4,6) 3(NH3)(NO)]. Crystal data: space group P21/n with a = 10.477(3), b = 26.359(5), c = 20.1 24(4) Å, β = 87.21(1)°, and Z = 4; 1 040 reflections giving R = 0.078. The complex againhas trigonal-bipyramidal geometry with apical NO and NH3 groups. The co-ordinated ammonia ligand arises from reduction of the co-ordinated hydroylamido-group.

Original languageEnglish (US)
Pages (from-to)967-973
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number5
DOIs
StatePublished - 1986
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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