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Group 6 Hexacarbonyls as Ligands for the Silver Cation: Syntheses, Characterization, and Analysis of the Bonding Compared with the Isoelectronic Group 5 Hexacarbonylates
Author(s) -
Bohnenberger Jan,
Kratzert Daniel,
Gorantla Sai Manoj N. V. T.,
Pan Sudip,
Frenking Gernot,
Krossing Ingo
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202003934
Subject(s) - chemistry , crystallography , singlet state , ligand (biochemistry) , group (periodic table) , atom (system on chip) , electronic structure , main group element , stereochemistry , computational chemistry , transition metal , atomic physics , organic chemistry , biochemistry , physics , receptor , computer science , embedded system , excited state , catalysis
The syntheses of the two novel complexes [Ag{Mo/W(CO) 6 } 2 ] + [F‐{Al(OR F ) 3 } 2 ] − (R F =C(CF 3 ) 3 ) are reported along with their structural and spectroscopic characterization. The X‐ray structure shows that three carbonyl ligands from each M(CO) 6 fragment bend towards the silver atom within binding Ag−C distance range. DFT calculations of the free cations [Ag{M(CO) 6 } 2 ] + (M=Cr, Mo, W) in the electronic singlet state give equilibrium structures with C 2 symmetry with two bridging carbonyl groups from each hexacarbonyl ligand. Similar structures with C 2 symmetry (M=Nb) and D 2 symmetry (M=V, Ta) are calculated for the isoelectronic group 5 anions [Ag{M(CO) 6 } 2 ] − (M=V, Nb, Ta). The electronic structure of the cations is analyzed with the QTAIM and EDA‐NOCV methods, which provide detailed information about the nature of the chemical bonds between Ag + and the {M(CO) 6 } 2 q ( q = −2, M = V, Nb, Ta; q = 0, M = Cr, Mo, W) ligands.