4 years ago

A Two-Coordinate Neutral Germylene Supported by a β-Diketiminate Ligand in the Radical State

A Two-Coordinate Neutral Germylene Supported by a β-Diketiminate Ligand in the Radical State
Anyang Li, Wenyuan Wang, Yinfeng Meng, Gengwen Tan, Yaoyu Wang, Sanping Chen, Xinmiao Wang, Zhen Wang, Lei Hou, Hecong Cheng, Xiaohua Lu
Using the new β-diketimine 1a (PhCH(PhC═N-Dip)2, Dip = 2,6-iPr2C6H3), which possesses three phenyl groups at the ligand backbone, we synthesized the β-diketiminato germylene chloride 2 (LGeCl, L = [PhC(PhCN-Dip)2]). The β-diketiminato germanium radical complex 3 (LGe:, L = [PhC(PhCN-Dip)2]2–) has been isolated by reduction of LGeCl with sodium/naphthalene in 64% yield. X-ray diffraction, HR-MS, and electron paramagnetic resonance analyses together with DFT calculations reveal that 3 exhibits a remarkably different structure in comparison with the reported Ge(I) radical C (L′Ge:, L′ = [HC(tBuCN-Dip)2]). The inductive effect of three phenyl groups leads to the backbone of ligand 1 being more electron deficient, and therefore the singly occupied molecular orbital (SOMO) of radical 3 is mainly composed of a π-antibonding orbital between the N and C atoms. This results in ca. 0.14 Å shorter N–Ge bonds and ca. 0.1 Å longer C–N bonds in 3 in comparison to those observed in C. Thus, the radical 3 is a two-coordinate germylene stabilized by an N-heterocyclic radical ligand.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00400

DOI: 10.1021/acs.organomet.7b00400

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