Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Palladium(I) Complexes†
Dr. Makoto Tanabe
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorShumpei Omine
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorNaoko Ishikawa
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kohtaro Osakada
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)Search for more papers by this authorYoshihiro Hayashi
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552 (Japan)
Search for more papers by this authorProf. Dr. Susumu Kawauchi
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552 (Japan)
Search for more papers by this authorDr. Makoto Tanabe
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorShumpei Omine
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorNaoko Ishikawa
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kohtaro Osakada
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-3 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)Search for more papers by this authorYoshihiro Hayashi
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552 (Japan)
Search for more papers by this authorProf. Dr. Susumu Kawauchi
Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552 (Japan)
Search for more papers by this authorThis work was financially supported by Grants-in-Aid for Scientific Research (No. 24350027) and (No. 25410061) from the Ministry of Education, Culture, Sports, Science and Technology of Japan. The numerical calculations were carried out on the TSUBAME 2.5 supercomputer at the Tokyo Institute of Technology, Tokyo (Japan), and on the supercomputer at the Research Center for Computational Science, Okazaki (Japan).
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 GeGe 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 PdGe 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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