Titanium Germylidenes

Vladimir Ya Lee; Ryo Sakai; Kazunori Takanashi; Olga A Gapurenko; Ruslan M Minyaev; Heinz Gornitzka; Akira Sekiguchi

doi:10.1002/anie.202015704

Titanium Germylidenes

Angew Chem Int Ed Engl. 2021 Feb 19;60(8):3951-3955. doi: 10.1002/anie.202015704. Epub 2021 Jan 26.

Authors

Vladimir Ya Lee¹, Ryo Sakai^{1

2}, Kazunori Takanashi^{1

3}, Olga A Gapurenko⁴, Ruslan M Minyaev⁴, Heinz Gornitzka⁵, Akira Sekiguchi^{1

6}

Affiliations

¹ Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571, Japan.
² Present address: Ueda Japan Radio Co., Ltd. (UJRC), Ueda, Nagano, 386-0032, Japan.
³ Present address: JSR Corporation, Yokkaichi-shi, Mie, 510-8552, Japan.
⁴ Institute of Physical and Organic Chemistry, Southern Federal University, Rostov on Don, 344090, Russian Federation.
⁵ LCC-CNRS, Université de Toulouse, CNRS, UPS, Toulouse, France.
⁶ Present address: Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, 305-8565, Japan.

PMID: 33289313
DOI: 10.1002/anie.202015704

Abstract

Two novel 18-electron titanium germylene complexes, Cp₂ Ti(L)=Ge[Si₃ (SiMe^t Bu₂ )₄ ] 3 b (L=Me₃ P) and 3 c (L=XylNC), were synthesized, isolated, and structurally characterized. The length of the titanium-germanium bonds of 2.5387(3) Å and 2.5276(3) Å (in 3 b and 3 c, respectively) well match those expected for the double bond, which was further supported by the DFT study. Based on their structural characteristics, as well as their atomic charges calculations which revealed Ti(δ+)=Ge(δ-) bond polarization, both 3 b and 3 c are classified as the Schrock-type titanium germylidenes, as the germanium analogues of the widely known titanium alkylidenes. By contrast, germylene complexes of the group 6 metals 8 a (M=Mo) and 8 b (M=W) are better described as Fischer-type germylene complexes.

Keywords: NMR spectroscopy; X-ray diffraction; density functional calculations; germanium; titanium.

Abstract

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