0000000000620622
AUTHOR
Thomas G. Hibbert
Sulfur, tin and gold derivatives of 1-(2'-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C2B10H10 (R = 2'-pyridyl, X = SH, SnMe3 or AuPPh3).
Reaction of the lithium salt of 1-(2'-pyridyl)-ortho-carborane, Li[1-R-1,2-C(2)B(10)H(10)](R = 2'-NC(5)H(4)), with sulfur, followed by hydrolysis, gave the mercapto-o-carborane, 1-R-2-SH-1,2-C(2)B(10)H(10) which forms chiral crystals containing helical chains of molecules linked by intermolecular S-H...N hydrogen bonds. The cage C(1)-C(2) and exo C(2)-S bond lengths (1.730(3) and 1.775(2)[Angstrom], respectively) are indicative of exo S=C pi bonding. The tin derivative 1-R-2-SnMe(3)-1,2-C(2)B(10)H(10), prepared from Li[1-R-1,2-C(2)B(10)H(10)] and Me(3)SnCl, crystallises with no significant intermolecular interactions. The pyridyl group lies in the C(1)-C(2)-Sn plane, oriented to minimise th…
Structural distortions in homoleptic (RE)4A (E = O, S, Se; A = C, Si, Ge, Sn): Implications for the CVD of tin sulfides
The structures of Sn(SBut)4 and Sn(SCy)4 have been determined and adopt S4 and D2 conformations respectively; the anion [(PhS)Sn3]−, as its Ph4P+ salt, has a structure approaching Cs symmetry. In all three compounds, there are large variations in the ∠S–Sn–S within the same molecule, which have been rationalised in terms of the C–S–Sn–S–C conformations. For Sn(SR)4, the ∠S–Sn–S increases as the conformations change from trans, trans to trans, gauche and gauche, gauche, as the number of eclipsed lone pairs decreases and this rationale is shown to be applicable to a variety of A(ER)4 (A = C, Si, Ge, Sn; E = O, S, Se) and related [Mo(SR)4, Ga(SR)4−] systems. AM1 calculations have been used to …
Synthesis and thermal decomposition studies of homo- and heteroleptic tin(iv) thiolates and dithiocarbamates: molecular precursors for tin sulfides
The syntheses and X-ray structures of novel heteroleptic thiolate/dithiocarbamate derivatives (Et2NCS2)2(RS)2Sn (R = Cy, CH2CF3) have been examined and their thermal decompositions compared with those of selected tin(II) and tin(IV) dithiocarbamates. The heteroleptic species decompose to SnS by initial elimination of RSSR to afford (Et2NCS2)2Sn and subsequent loss of [Et2NC(S)]2S. In contrast, (Et2NCS2)4Sn decomposes via [(Et2NCS2)2SnS]2, whose structure has been determined, and finally to SnS2 by sequential elimination of [Et2NC(S)]2S. The two families of compounds, (R2NCS2)4Sn and (Et2NCS2)2(RS)2Sn, thus provide single-source materials for bulk SnS2 and SnS, respectively, by virtue of the…