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The Additive Nature of Energy Penalties in 10‐Vertex nido ‐(Car)boranes
Author(s) -
Kiani Farooq A.,
Hofmann Matthias
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200400982
Subject(s) - boranes , chemistry , carborane , vertex (graph theory) , hydride , density functional theory , boron , computational chemistry , bond dissociation energy , cluster (spacecraft) , molecule , stereochemistry , organic chemistry , combinatorics , graph , metal , mathematics , computer science , programming language
A structural increment system, i.e. quantitative rules that govern the relative stabilities of 10‐vertex nido ‐boranes and‐carboranes, has been determined. Density functional theory computations at the B3LYP/6‐311+G(d,p)//B3LYP/6‐31G(d) level with ZPE corrections were carried out for 81 different boron hydride and carborane structures from [B 10 H 12 ] 2– to C 3 B 7 H 11 to determine their relative stabilities. A set of eleven disfavored geometrical features that destabilize a cluster structure relative to a hypothetical ideal situation were identified and weighted by so‐called energy penalties. The latter show good additive behavior and allow us to reproduce the DFT computed relative energies mostly with an accuracy of 6.0 kcal mol –1 . Some unknown 10‐vertex nido‐ carboranes that are thermodynamically more stable than their known isomers are also identified. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)