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Titanium Germylidenes.
Vladimir Ya Lee1, Ryo Sakai1,2, Kazunori Takanashi1,3
1Department of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571, Japan.
Angewandte Chemie (International Ed. in English)
|December 8, 2020
Summary
Two novel titanium germylene complexes were synthesized and characterized. These compounds are classified as Schrock-type titanium germylidenes, distinct from Fischer-type complexes.
Area of Science:
- Organometallic Chemistry
- Main Group Chemistry
- Coordination Chemistry
Background:
- Germylene complexes are important in inorganic and organometallic chemistry.
- Titanium alkylidenes are well-established, but titanium germylidenes are less explored.
- Distinguishing between Schrock-type and Fischer-type carbene/germylene complexes is crucial for understanding bonding and reactivity.
Purpose of the Study:
- To synthesize and characterize novel 18-electron titanium germylene complexes.
- To investigate the bonding and electronic properties of titanium-germanium bonds.
- To classify the synthesized complexes as either Schrock-type or Fischer-type.
Main Methods:
- Synthesis and isolation of titanium germylene complexes.
- Single-crystal X-ray diffraction for structural characterization.
- Density Functional Theory (DFT) calculations for bond analysis and charge distribution.
Main Results:
- Two novel 18-electron titanium germylene complexes, Cp2Ti(L)=Ge[Si3(SiMetBu2)4] (L=PMe3, 3b; L=CNXyl, 3c), were successfully synthesized and characterized.
- X-ray crystallography revealed Ti-Ge bond lengths consistent with double bond character (2.5387(3) Å for 3b, 2.5276(3) Å for 3c).
- DFT calculations supported double bond character and indicated significant Ti(δ+)=Ge(δ-) bond polarization.
Conclusions:
- The synthesized titanium complexes, 3b and 3c, are classified as Schrock-type titanium germylidenes.
- These complexes represent the germanium analogues of known titanium alkylidenes.
- The findings highlight a contrast with group 6 metal germylene complexes, which are better described as Fischer-type.
