A Bis(silylenyl)pyridine Zero‐Valent Germanium Complex and Its Remarkable Reactivity. Issue 48 (2nd November 2016)

• Record Type: Journal Article
• Authors: Zhou, Yu‐Peng; Karni, Miriam; Yao, Shenglai; Apeloig, Yitzhak; Driess, Matthias
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 48(2016)
• Page Start: 15096
• Page End: 15099
• Publication Date: 2016-11-02
• Subjects: germanium -- metallylenes -- pincer ligands -- silicon -- silylene; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201609520
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The synthesis, reactivity, and electronic structure of the unique germylone iron carbonyl complex[SiNSi]Ge 0 →Fe(CO)4 is reported. The compound was obtained in 49 % yield from the reaction of the bis(N‐heterocyclic silylenyl)pyridine pincer ligandSiNSi (1, 6‐C5 NH3 ‐[EtNSi(N t Bu)2 CPh]2 ) with GeCl2 ⋅(dioxane) to give the corresponding chlorogermyliumylidene chloride precursor[SiNSi]Ge II Cl + Cl −, which was further reduced with K2 Fe(CO)4 . Single‐crystal X‐ray diffraction analysis of[SiNSi]Ge →Fe(CO)4 revealed that the Ge 0 center adopts a trigonal‐pyramidal geometry with a Si‐Ge‐Si angle of 95.66(2)°. Remarkably, one of the Si II donor atoms in the complex is five‐coordinated because of additional (pyridine)N→Si coordination. Unexpectedly, the reaction of[SiNSi]Ge →Fe(CO)4 with GeCl2 ⋅(dioxane) (one molar equivalent) yielded the first push–pull germylone–germylene donor–acceptor complex, [SiNSi]Ge →GeCl2 →Fe(CO)4 through the insertion of GeCl2 into the dative Ge 0 →Fe bond. The electronic features of the new compounds were investigated by DFT calculations. Abstract : Germanium‐enriched : The synthesis and unusual chemical and electronic properties of the first zero‐valent germanium ("germylone") iron complex[SiNSi] GeFe(CO)4 are reported. This complex was further transformed into an unprecedented mixed‐valent push–pull Ge 0 →GeCl2 complex.