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18‐electron rule and the 3c/4e hyperbonding saturation limit
Author(s) -
Landis C. R.,
Weinhold F.
Publication year - 2016
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24001
Subject(s) - saturation (graph theory) , limit (mathematics) , electron , statistical physics , atomic physics , physics , mathematics , nuclear physics , mathematical analysis , combinatorics
We show that the empirical 18‐electron rule of transition metal chemistry corresponds to an intrinsic saturation limit for the 3c/4e hyperbonding interactions that are a ubiquitous feature of D‐block aggregation phenomena. Such a “rule” therefore requires no “p‐orbital participation,” “d 2 sp 3 hybridization,” “valence shell expansion,” or other p‐type intrusions into the Aufbau orbital filling sequence. Instead, 18e stability corresponds to the natural terminus of post‐Lewis 3c/4e resonance‐type stabilizations that lead to successive ligand additions (and formal increments of electron count) at a transition metal center, all within the normal (s + 5d) confines of D‐block valence space. © 2015 Wiley Periodicals, Inc.