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Mono‐ and Dicoordinate Germanium(0) as a Four‐Electron Donor
Author(s) -
Mandal Debdeep,
Dhara Debabrata,
Maiti Avijit,
Klemmer Lukas,
Huch Volker,
Zimmer Michael,
Rzepa Henry S.,
Scheschkewitz David,
Jana Anukul
Publication year - 2018
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.201800071
Subject(s) - germanide , carbene , germanium , chemistry , crystallography , ligand (biochemistry) , stoichiometry , natural bond orbital , carbon monoxide , steric effects , stereochemistry , density functional theory , computational chemistry , catalysis , organic chemistry , silicon , receptor , biochemistry
We report the synthesis and isolation of molecular iron germanide motifs in the stoichiometry of Fe 3 Ge and Fe 2 Ge, which are stabilized by the coordination of N‐heterocyclic carbene (NHC) and carbon monoxide (CO) ligands. NHCi Pr2 Me2⋅Ge[Fe(CO) 4 ][Fe 2 (CO) 8 ] (NHCi Pr2 Me2=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene), a germanium(0) ligand with just one NHC as an auxiliary ligand, assumes a bridging coordination mode between a mononuclear [Fe(CO) 4 ] and a dinuclear [(CO) 4 FeFe(CO) 4 ] unit with rapid exchange between the two binding modes in solution. The electronic structure of this species is analysed by NBO and ELF calculations with DFT methods, as well as the mechanistic details of its fluxional coordination behaviour. Treatment of NHCi Pr2 Me2⋅Ge[Fe(CO) 4 ] [Fe 2 (CO) 8 ] with the sterically less demanding NHCMe4(NHCMe4=1,3,4,5‐tetramethylimidazol‐2‐ylidene) leads to a dinuclear iron complex (NHCMe4) 2 Ge[Fe(CO) 4 ] 2 that contains a bridging germylone ligand with two stabilizing NHC equivalents.