Synthesis,characterization and crystal structures of organolead dithiolate compounds displaying transannular interactions D···Pb (D = O,S)

Treatment of Ph₂PbCl₂ with O(C₆H₄SH)₂ (1a), S(C₆H₄SH)₂ (2a) and S(C₆H₃SH)₂O (3a) afforded the stable organolead compounds [{O(C₆H₄S)₂}PbPh₂] (1b), [{S(C₆H₄S)₂}PbPh₂] (2b) and [{S(C₆H₃S)₂O}PbPh₂] (3b). X-ray structure determinations of dithiolate-diphenyl lead compounds 1b–3b revealed that the trichalcogenated ligands are tridentate in 1b and 2b, and bidentate in 3b. The lead atom acts as an acceptor atom exhibiting weak intramolecular transannular interactions with the donor D atom, with tetrahedral distortions of 48% for 1b, 51% for 2b and 45% for 3b. The local geometry at the lead atom is described as monocapped tetrahedral. The crystal packing of title compounds is stabilized by several non-bonded interactions.     

Pentacoordination at antimony in dibenzostibocines via D–Sb transannular interactions (D = O,S): A structural study

Addition of M₂SCN(CH₂R)₂ to D(C₆H₄S)₂SbCl in methylene chloride solution leaded to the formation of the stable compounds D(C₆H₄S)₂SbS₂CN(CH₂R)₂ (D = O, R = Me, 1; D = S, R = Me, 2; R = Ph, 3). The new dibenzostibocines derivatives containing two different types of dithioligands were characterized by elemental analysis and spectroscopic studies (IR, ¹H and ¹³C NMR). Single crystal X-ray diffraction determinations of complexes 1–3 revealed that the antimony atom acts as an acceptor atom exhibiting an intramolecular transannular interaction with the donor D atom, expanding its coordination from three to five and displaying a skew trapezoidal local geometry.     

Hexacoordinated spirocyclic germanium(IV) complex: Synthesis and structural characterization

The spiro‐dibenzogermocine [O(o‐C₆H₄S)₂]₂Ge ( 1 ) was prepared in a reaction between O(o‐C₆H₄SH)₂ and Ge(OⁱPr)₄, and its molecular structure was determined by X‐ray diffraction studies. In the solid state, 1 shows the existence of two weak O → Ge transannular interactions, resulting in a hexacoordinated germanium atom that displays the geometry of a distorted bicapped tetrahedron. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:45–49, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20510     

Nonconventional C–H···Cu Interaction Between Copper Cun Clusters (n = 3–20) and Aromatic Compounds

The present study examines bonding patterns between copper Cu_n clusters (n?=?3–20) and aromatic compounds (benzene, phenol, and benzaldehyde) using a density-functional theory (DFT) approach. Hirshfeld population, natural bond orbital (NBO), molecular orbitals, and quantum theory of atoms in molecules (QTAIM) analyses suggested the formation of two types of interactions Cu–arene and C–H···Cu, in the complexation of copper clusters by an aromatic compound.

     

Hypervalence at tin(IV) by transannular bonding of sulfur in an eight-membered ring: The case of dibenzostannocines [{S(C6H4S)2}Sn]

Treatment of Ph₂SnCl₂ with S(C₆H₄SH)₂ in benzene leaded to the formation of [{S(C₆H₄S)₂}SnPhCl] (1); the same reaction with 1,4-diazabicyclo-[2.2.2]-octane leaded [{S(C₆H₄S)₂}SnPh₂] (4). The compounds [{S(C₆H₄S)₂}SnPhHal] (Hal = Br, 2; I, 3) have been synthesized by halogen exchange from 1 and the corresponding potassium halide. The compound [{S(C₆H₄S)₂}SnCl₂] (5) was obtained from S(C₆H₄SH)₂ and SnCl₄. The reaction of 1 with NaS₂CNEt₂·3H₂O yielded [{S(C₆H₄S)₂}SnPh{S₂CNEt₂}] (6). X-ray structure determinations of dibenzostannocines 1–6 revealed that the tin atom acts as an acceptor atom displaying an intramolecular transannular interaction with the sulfur (thioether-like) atom. The local geometry of the Sn atom in the compounds 1–5 is described as distorted trigonal bipyramidal with a TBP character spanning from 81% to 73%. In 6 the tin atom is six-coordinate with a distorted octahedral geometry.