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Synthesis, Characterizations, and Structure of Group 4 Metallocene Complexes of Some Difunctional Ligands Containing Oxygen and Sulfur Donors
Author(s) -
Lin ShowJinn,
Ho YuhCho,
Gau HanMou
Publication year - 1999
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199900073
Subject(s) - chemistry , thioether , monoclinic crystal system , alkoxide , metallocene , stereochemistry , monomer , crystallography , crystal structure , metal , medicinal chemistry , polymer chemistry , polymerization , organic chemistry , catalysis , polymer
Abstract Reactions of CH 3 OCH 2 CH 2 OH, PhOCH 2 CH 2 OH, o ‐CH 3 OC 6 H 4 CH 2 OH, or PhSCH 2 CH 2 OH with Cp 2 ZrCl 2 in the presence of NEt 3 gave series monomeric complexes Cp 2 ZrClX (X = OCH 2 CH 2 OCH 3 ( 1 ), OCH 2 CH 2 OPh ( 2 ), o ‐OCH 2 C 6 H 4 OCH 3 ( 3 ) or OCH 2 CH 2 SPh ( 4 )). In a reaction of Cp 2 TiCl 2 with PhSCH 2 CH 2 OH in the presence of NEt 3 , the complex Cp 2 TiCl(OCH 2 CH 2 SPh) ( 5 ) was obtained. These complexes were characterized by the 1 H and 13 C NMR, and the chemical shifts of the Cp rings for complexes 1–4 are nearly identical, despite differences in ligands for an indication of similar structures of these complexes around the metal center. Complex 4 crystallizes into the monoclinic P2 1 /c space group with a = 13.806(3) Å, b = 16.394(3) Å, c = 7.838(2) Å, β = 100.85(3)° Z = 4, R = 0.029, R w = 0.044, and Gof = 1.19. The molecular structure of complex 4 shows that the 2‐(phenylthio)ethoxide bonds to the Zr metal center through the alkoxide donor leaving the thioether donor free from coordination.