Calculations on indium and thallium cyclopentadienyls.: Metal-metal interactions and possible new species

被引：36

作者：

Pyykkö, P ^{[1
]}

Straka, M ^{[1
]}

Tamm, T ^{[1
]}

机构：

[1] Univ Helsinki, Dept Chem, FIN-00014 Helsinki, Finland

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 1999年 / 1卷 / 15期

关键词：

D O I：

10.1039/a903008e

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The possibility of an attractive interaction between two closed-shell molecules containing In(I) or Tl(I) was studied using relativistic pseudopotentials and correlated ab initio methods ranging from MP2 to CCSD(T). The results for the simple test system (TlH)(2) qualitatively agree with earlier ones by Schwerdtfeger (Inorg. Chem., 1991, 30, 1660). The calculated dimerization energy is -20 kJ mol(-1). The results for the more realistic [M(eta(5)-Cp)](2) model (M=In, Tl; Cp=cyclopentadiene, C5H5) yield a weaker attraction of about - 12 and - 16 kJ mol(-1), respectively. The M-M secondary bond lengths are somewhat longer and the M-M-Cp angles more acute than in the dimers found in solids. This is attributed to the crystal effects. The calculated structures for [M(eta(5)-Cp)(2)](-) anions agree with experimental ones for the known M=Tl case. Predicted structures are given for the [M(eta(5)-Cp-2)](+) cations and for a hypothetical M(eta(5)-Cp)(3).

引用

页码：3441 / 3444

页数：4

共 38 条

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