title: Theoretical study of structure, bonding, and electronic behavior of low-valent bismuth cyclopentadienyl and pentamethylcyclopentadienyl half-sandwich compounds.
abstract: The correlations between structural and electronic properties of the bismuth cyclopentadienyl complexes of the types [(C(5)R(5))(n)Bi(n)](q+) (where R = H, Me; n = 1, q = 2; n = 1-4, q = 0) and (C(5)R(5))BiX(2) (where R = H, Me; X = Cl, Br, I) were studied with quantum-chemical calculations. The influence of the ligand, significant variations in the Bi-C bond lengths, haptotropic shifts with distortion of the C(5)R(5) ring, Jahn-Teller splitting, interstabilization effects, and the role of the lone pairs on p-block element-unalkylated or peralkylated cyclopentadienyl ring interactions were examined to obtain qualitative and quantitative pictures of the intramolecular C(5)R(5)-Bi interactions. Our theoretical investigations of monovalent and trivalent bismuth cyclopentadienyl complexes give an insight into the geometric and electronic structures, the relative stabilities and further behavior of this kind of compounds.
authors.affiliation: Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
authors.forename: Kirill Yu
authors.initials: KY
authors.lastname: Monakhov
authors.forename: Gerald
authors.initials: G
authors.lastname: Linti