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Titanium Germylidenes
Author(s) -
Lee Vladimir Ya.,
Sakai Ryo,
Takanashi Kazunori,
Gapurenko Olga A.,
Minyaev Ruslan M.,
Gornitzka Heinz,
Sekiguchi Akira
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202015704
Subject(s) - titanium , germanium , chemistry , crystallography , bond length , metal , titanio , chemical bond , stereochemistry , transition metal , crystal structure , silicon , organic chemistry , catalysis
Abstract Two novel 18‐electron titanium germylene complexes, Cp 2 Ti(L)=Ge[Si 3 (SiMe t Bu 2 ) 4 ] 3 b (L=Me 3 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.