Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Palladium(I) Complexes |
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| Authors: | Dr. Makoto Tanabe Shumpei Omine Naoko Ishikawa Prof. Dr. Kohtaro Osakada Yoshihiro Hayashi Prof. Dr. Susumu Kawauchi |
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| Affiliation: | 1. Chemical Resources Laboratory, Tokyo Institute of Technology, 4259‐R1‐3 Nagatsuta, Midori‐ku, Yokohama 226‐8503 (Japan);2. Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152‐8552 (Japan) |
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| Abstract: | ![]()
The dinuclear palladium(I) complexes [L(Ar2HGe)Pd(μ‐GeAr2)2Pd(GeHAr2)L] (Ar=Ph, p‐Tol; L=PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge???Ge bond lengths of 2.8263(4) Å (L=PMe3) and 2.928(1) Å (L=tBuNC), which are close to the longest Ge? Ge bond reported to date [2.714(1) Å]. Significant Ge???Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge???Ge interaction, and simultaneously activates two Pd? Ge bonds. Adding the chelating diphosphine 1,2‐bis(diethylphosphino)ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane. |
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| Keywords: | bridging ligands density functional calculations germanium ligand effects P ligands |
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