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Condensed polyhedral boranes and analogous organometallic clusters: a molecular orbital and density functional theory study on the cap–cap interactions
Author(s) -
Jemmis Eluvathingal D.,
Pancharatna Pattath D.
Publication year - 2003
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.462
Subject(s) - antibonding molecular orbital , chemistry , boranes , borane , crystallography , molecular orbital , density functional theory , atomic orbital , molecule , computational chemistry , agostic interaction , atom (system on chip) , boron , stereochemistry , electron , physics , organic chemistry , quantum mechanics , metal , catalysis , biochemistry , computer science , embedded system
The interactions between the non‐bonded atoms on adjacent units were assumed to be one of the major factors that hinder the exploration and advancement of macropolyhedral borane chemistry. In sandwich complexes involving boron as the bridging atom, the interaction between non‐bonded atoms tends to be antibonding, but a closer analysis of various condensed systems shows that this cannot be generalized. The overlap populations (OPs) calculated for structures optimized at the B3LYP/6‐31g* level [B 21 H 18 1− ( 5 ), B 20 H 16 ( 6 ), [Al(C 2 B 4 H 6 ) 2 ] 1− ( 7 ), B 12 H 10 2− ( 8 ), B 10 H 8 2− ( 9 and 14 ), B 11 H 13 ( 10 ), B 10 H 14 ( 11 ), C 2 B 8 H 12 ( 13 ) and B 20 H 18 2− ( 15 )] indicate bonding interactions between the caps, except for 7 and 13 . This is substantiated by a detailed extended Hückel‐based molecular orbital (MO) study using B 10 H 14 as a model system to represent macropolyhedral boranes with higher fusions. An isolobal equivalent structure, [C 8 H 6 (Ru(CO) 2 Me) 2 ] ( 17 ), studied at the B3LYP/LANL2DZ level has weak RuRu interactions. An analysis of the nature of the MOs in B 10 H 14 ( 11 ) shows that there is no direct head on overlap of the cap orbitals that are antibonding; this is in contradiction to sandwiched molecules ( 7 ), where there are two occupied MOs with antibonding interactions. The m + n + o electron pair count ( m is the number of cages involved in condensation, n is the number of vertices and o is the number of single vertex condensations) of sandwich complexes requires the filling of these two MOs. The negative OP between the carbon atoms in 13 is attributed to the greater electronegativity of carbon and is substantiated by a fragment MO analysis. Copyright © 2003 John Wiley & Sons, Ltd.