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A theoretical study of the bonding capabilities of the zinc‐zinc double bond
Author(s) -
Ayala Regla,
Galindo Agustín
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25823
Subject(s) - zinc , chemistry , molecule , covalent bond , crystallography , metal , delocalized electron , transition metal , moiety , bond length , ethylene , inorganic chemistry , stereochemistry , organic chemistry , catalysis
The theoretical knowledge about the zinc‐zinc bond has been recently expanded after the proposal of a zinc‐zinc double bond in several [Zn 2 (L) 4 ] compounds ( Angew. Chem. Int. Ed. 2017 , 56 , 10151‐10155). Prompted by these results, we have selected the [Zn 2 (CO) 4 ] species, isolobally related to ethylene, and theoretically investigated the possible η 2 ‐ Zn 2 ‐coordination to several first‐row transition metal fragments. The [Zn 2 (CO) 4 ] coordination to the metal fragment produces an elongation of the dizinc bond and a concomitant pyramidalization of the [Zn(CO) 2 ] unit. These structural parameters are indicative of π‐backdonation from the metal to the coordinated dizinc moiety, as occurred with ethylene ligand. A quantum theory of atoms in molecules study of the ZnZn bond shows a decrease of ρ BCP , ∇ 2 ρ BCP ∫ Zn∩Zn ρ and delocalization indexes δ(Zn,Zn), relative to corresponding values in the parent [Zn 2 (CO) 4 ] molecule. The ZnZn and MZn bonds in these [(η 2 ‐Zn 2 (CO) 4 )M(L) n ] complexes can be described as shared interactions with an important covalent component where the ZnZn bond is preserved, albeit weakened, upon coordination.