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Electrophilic Attack on Tetrahedral Metal Complexes
Author(s) -
Silvestre Jerome,
Albright Thomas A.
Publication year - 1983
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.198300020
Subject(s) - chemistry , square pyramid , tetrahedron , electrophile , trigonal bipyramidal molecular geometry , crystallography , ionic bonding , atom (system on chip) , metal , bipyramid , molecular orbital , computational chemistry , stereochemistry , ion , molecule , crystal structure , organic chemistry , computer science , embedded system , catalysis
Abstract A number of ML 4 Lî complexes exist where Lî contains an electropositive atom connected to the transition metal. The structures of these compounds are very distorted; they do not correspond to a trigonal bipyramid, square pyramid or somewhere between these two extremes. An electronic rationale for these alternative structures is presented with the aid of molecular orbital calculations of the extended Hückel type. It is shown that in these compounds the M‐Lî bond is quite ionic in the sense of Lî + ML − 4 . The deformation is then due, in part, to the tendency of ML − 4 to adopt a tetrahedral arrangement. Furthermore, it is shown that an electrophile (Lî + ) may attack a three‐fold face, two‐fold edge, or somewhere intermediate at the tetrahedral ML − 4 group yielding an alternative structure for these five‐coordinate complexes.