Copper(I) complexes of sterically-hindered 2-pyridinethione ligands. Crystal structures of [CuCl(2-SC5H2NH-3-SiMe3-6-SiEt3)2] and the disulfide, [-2-SC5H2N-3,6-(SiMe2But)2]2

Eric Block, Gabriel Ofori-Okai, Kang Hyunkyu, Jon A Zubieta

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Abstract

The reactions of Cu(II)X2 species (X=Cl-, NO3 -) with 3-(triorganosilyl)pyridine-2-thiois and 3,6- (triorganosilyl)pyridine-2-thiols were investigated. When the less sterically hindered 3-(triorganosilyl)pyridine-2-thiol ligands were used, Cu(I) species of the type [Cu(2-SC5H3NH-3-SiR3)3]+ were isolated. In contrast, use of the sterically demanding ligands (SC5H2NH-3-SiMe3-6-SiEt3) and (SC5H2NH-3,6- SiMe2But) yielded the Cu(I) species [Cu(2-SC5H2NH-3-SiMe3-6-SiEt3)2Cl] (2) and [Cu(2-SC5H2NH- 3,6-SiMe3But)2Cl] (3). The sulfur ligands are present as monodentate donors in the neutral thione form, protonated at the pyridine nitrogen. The isolation of 3,3′, 6,6′-tetrakis(dimethyl-tert-butylsilyl)pyridyl disulfide (4) confirms the role of the thiolates as reductants in the synthesis of the Cu(I) complexes. Crystal data: [Cu(2-SC5H2NH-3-SiMe3-6-SiEt3)2Cl] (2), monoclinic P21/c, a=16.845(3), b=13.421(2), c=17.288(3) Å, β=92.46(1)°, V=3904.8 Å3, Z=4, Dcalc=1.18 g cm-3. Structure refinement and solution based on 1810 reflections converged at 0.065. C34H64N2Si4S2 (4), orthorhombic Pbcn, a=12.720(2), b=15.521(3), c=21.162(3) Å, V=4177.8(10) Å3, Z=4, Dcalc=1.07 g cm-3, 2290 reflections, R=0.058.

Original languageEnglish (US)
Pages (from-to)59-65
Number of pages7
JournalInorganica Chimica Acta
Volume187
Issue number1
DOIs
StatePublished - Sep 2 1991

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ASJC Scopus subject areas

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

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