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
1991; Elsevier BV; Volume: 187; Issue: 1 Linguagem: Inglês
10.1016/s0020-1693(00)82977-1
ISSN1873-3255
AutoresEric Block, Gabriel Ofori‐Okai, Hyunkyu Kang, Jon Zubieta,
Tópico(s)Organometallic Compounds Synthesis and Characterization
ResumoThe 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.
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