The effects of steric hindrance on the chemistry of rhenium and molybdenum nitrosyl thiolato-complexes. The structures of[Mo(SC6H2Pr3 i)3(NH3(NO)] and [Re(SC6H3Pr2 i)4(NO)]

P. J. Blower, P. T. Bishop, J. R. Dilworth, T. C. Hsieh, J. Hutchinson, T. Nicholson, Jon A Zubieta

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Abstract

The Re(II) nitrosyl complex [ReCl2(OMe)(NO)(PPh3)2] reacts with excess 2,6-Pr2 iC6H3S-(DIPT-) in methanol to give the Re(III) complex [Re(DIPT)4(NO)] (I) whereas thiophenolate gives a thiolatobridged Re(II) dimer. Crystal data for(I): crystallizes in the orthorhombic space group Pbca, a = 13.218(6) Å, b = 19.534(9) Å, c = 38.115(13) Å, V = 9841.3(6) Å3 to give Dcalc = 1.35 g cm-3 for Z = 8. Structure solution and refinement are based on 3047 reflections with Io>3σ|Io| and yielded a final R value of 0.064. The overall geometry about Re is trigonal bipyramidal with an apical NO group with a nearly linear ReNO system (ReNO, 173.6(14)°). The polymeric species '{Mo(NO)(NH2O)}n' reacts with excess 2,4,6-Pr3 iC6H2S-(TIPT- to give[Mo(TIPT)3(NH3)(NO)]·C5H12 (II) (C5H12 = n-pentane) whereas thiophenolate anion gives [Mo(SPh)4(NO)]-. Crystal data for (II): space group P21/n with a = 10.477(3) Å, b = 26.359(5) Å, c = 20.124(4) Å, β = 87.21(1)°, with V = 5550.9(12) Å3 to give Dcalc = 1.05 g cm-3 for Z = 4. Structure refinement was based on 1040 reflections with Io>3σ|Io| and yielded a final R value of 0.079. The geometry about Mo is again trigonal bipyramidal with apical NO and NH3 groups and again an essentially linear MoNO system (MNO = 174.2(3)°).

Original languageEnglish (US)
Pages (from-to)63-65
Number of pages3
JournalInorganica Chimica Acta
Volume101
Issue number1
DOIs
StatePublished - Jun 17 1985
Externally publishedYes

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ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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