A Bis(silylenyl)pyridine Zero-Valent Germanium Complex and Its Remarkable Reactivity.
The synthesis, reactivity, and electronic structure of the unique germylone iron carbonyl complex [SiNSi]Ge0→Fe(CO)4is reported. The compound was obtained in 49 % yield from the reaction of the bis(N-heterocyclic silylenyl)pyridine pincer ligand SiNSi (1,6-C5NH3-[EtNSi(NtBu)2CPh]2) with GeCl2⋅(dioxane) to give the corresponding chlorogermyliumylidene chloride precursor [SiNSi]GeIICl+Cl-, which was further reduced with K2Fe(CO)4. Single-crystal X-ray diffraction analysis of [SiNSi]Ge→Fe(CO)4revealed that the Ge0center adopts a trigonal-pyramidal geometry with a Si-Ge-Si angle of 95.66(2)°. Remarkably, one of the SiIIdonor atoms in the complex is five-coordinated because of additional (pyridine)N→Si coordination. Unexpectedly, the reaction of [SiNSi]Ge→Fe(CO)4with GeCl2⋅(dioxane) (one molar equivalent) yielded the first push-pull germylone-germylene donor-acceptor complex, [SiNSi]Ge→GeCl2→Fe(CO)4through the insertion of GeCl2into the dative Ge0→Fe bond. The electronic features of the new compounds were investigated by DFT calculations.
Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623, Berlin, Germany.
Yu-Peng
YP
Zhou
Schulich Department of Chemistry and the Lise Meitner Minerva Center for Computational Chemistry, Technion, Israel Institute of Technology, Haifa, 32000, Israel.
Miriam
M
Karni
Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623, Berlin, Germany.
Shenglai
S
Yao
Schulich Department of Chemistry and the Lise Meitner Minerva Center for Computational Chemistry, Technion, Israel Institute of Technology, Haifa, 32000, Israel.
Yitzhak
Y
Apeloig
Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623, Berlin, Germany.
Matthias
0000-0002-9873-4103
M
Driess
germanium; metallylenes; pincer ligands; silicon; silylene