Sulfur, tin and gold derivatives of 1-(2′-pyridyl)-ortho-carborane, 1-R-2-X-1,2-C₂B₁₀H₁₀(R = 2′-pyridyl, X = SH, SnMe₃or AuPPh₃)

Abstract

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Synthesis, spectroscopy and structures of palladium(II) and platinum(II) complexes containing mercapto-o-carborane

“…The C-C bond length in carboranes is sensitive to the nature of attached sulfur atom. The C-C distances in Cb°-SH, Cb°-SPh and Cb°-S À are 1.720, 1.708 and 1.836 Å, respectively [32][33][34]. The C-C distances in our complexes lie in the range 1.741(8)-1.777(2) Å which are slightly shorter than the one reported in Cb°-S À anion.…”

“…Similarly the Pd-P distances in 1 and 5 are shorter by $0.1 Å than 4 owing to the strong trans influence of the phosphine in the latter. The C-S distances in all these complexes vary between 1.763(6) and 1.795 (6) Å, which can be compared with those reported in Cb°-SH (1.776 Å) and Cb°-SPh (1.784 Å) [32,33]. The C-C bond length in carboranes is sensitive to the nature of attached sulfur atom.…”

Regioselective Insertion of o‐Carborynes into the α‐CH Bond of Tertiary Amines: Synthesis of α‐Carboranylated Amines

“…[8,10] Despite the remarkable progress in carborane chemistry, straightforward and general synthesis of such aminoalkyl o-carboranes still represents a challenging task. [11] Herein, we describe a highly regioselective a-carboranylation of tertiary amines for the convenient synthesis of 1-aminoalkyl-ocarboranes.…”

Preparative and structural studies on sulfur-linked carborane icosahedra: 2-Phenyl-ortho-carboranyl-sulfur systems (2-Ph-1,2-C2B10H10)2X (X=S, S2 or SO), and ortho-carboran-di-yl systems (1,2-C2B10H10Y)2 (Y=S or SO)

“…The C-S-C angle in 1 (112.8 (1) o ) is significantly greater than the C-S-S angle in 2 (105.5 (2) o ) which is due to steric repulsion between the two cages. Intramolecular B-H..H-B distances between the two cages are 2.27, 2.40 and 2.49 Å. Interestingly, the C(1)-C(2) bond lengths in 2 is some 0.03 Å longer than in PyCb o SH (X-ray 23 ) and PhCb o SH (calc 11 ) which suggests that the disulfur bridge (S-S) is a more effective π-bond donor to the ortho-carborane cage than is a thiol (S-H) group. (Table 1), differ from those in 1 and 2,though less than expected.…”