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Facial vs. Meridional Coordination Modes in Re I Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand
Author(s) -
Maser Leon,
Vogt Matthias,
Langer Robert
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100151
Subject(s) - deprotonation , isomerization , cationic polymerization , zonal and meridional , ligand (biochemistry) , chemistry , reactivity (psychology) , stereochemistry , coordination complex , crystallography , ion , medicinal chemistry , catalysis , polymer chemistry , physics , metal , receptor , medicine , biochemistry , alternative medicine , organic chemistry , atmospheric sciences , pathology
The reactivity of the novel cationic ligand precursor [(dppm) 2 CH](PF 6 ) ( 1 ) with a weakly coordinating anion and [ReBr(CO) 5 ] is reported. The initial coordination results in the formation of the facially coordinated dicationic complex fac‐ [({dppm} 2 CH)Re(CO) 3 ]X 2 ( fac‐ 2 , X=Br, PF 6 ). The facial coordination mode is retained in fac‐ [({dppm} 2 C)Re(CO) 3 ](PF 6 ) ( fac‐ 3 ) upon deprotonation of the central cationic donor group. Quantum chemical investigations indicate that for both complexes, 2 and 3 , the meridional coordination mode is thermodynamically favored. In line with these findings, the isomerization of the facially coordinated complex fac‐ 3 to the meridionally coordinated complex mer‐ [({dppm} 2 C)Re(CO) 3 ](PF 6 ) ( mer‐ 3 ) is observed under irradiation with UV‐light.