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Titanium Complexes Containing a Disulfide‐Bridged Bis(phenolato) Ligand: Synthesis and Structural Characterization of Three Different Bonding Modes
Author(s) -
Okuda Jun,
Fokken Stefan,
Kleinhenn Thomas,
Spaniol Thomas P.
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200006)2000:6<1321::aid-ejic1321>3.0.co;2-u
Subject(s) - chemistry , ligand (biochemistry) , titanium , octahedron , crystallography , dimer , coordination sphere , crystal structure , stereochemistry , organic chemistry , receptor , biochemistry
A series of titanium(IV) complexes containing the 2,2′‐dithiobis(6‐ tert ‐butyl‐4‐methylphenolato) ligand (dtbmp) were synthesized and characterized. Treatment of titanium tetra(isopropoxide) with 2,2′‐dithiobis(6‐ tert ‐butyl‐4‐methylphenol) (dtbmpH 2 ) gave, regardless of the molar ratio of the starting materials, a C 2 ‐symmetric dinuclear complex [Ti 2 (O i Pr) 2 (μ 2 ‐O i Pr) 2 (dtbmp)]. According to the results of a single crystal X‐ray analysis, the two Ti(O i Pr) 2 fragments in this complex are bridged by a dtbmp ligand and two isopropoxide ligands. The disulfide link of the dtbmp ligand is bonded to each of the titanium centers [Ti−S 2.795(1) and 2.768(1) Å], thus completing an octahedral coordination sphere around titanium. Reaction of [Ti 2 (O i Pr) 4 (μ 2 ‐O i Pr) 2 (dtbmp)] with Me 3 SiX (X = Br, I) gave the mononuclear complex Ti(dtbmp)X 2 . Crystallographic study revealed a distorted octahedral coordination with the disulfide link of the dtbmp dihapto‐bonded through a relatively short Ti−S distance of 2.637(1) Å (X = Br) or 2.645(2) Å (X = I). Finally, the reaction of titanium tetra( n ‐butoxide) with dtbmpH 2 gave a C i ‐symmetric dimer [Ti 2 (O n Bu) 2 (μ 2 ‐O n Bu) 2 (dtbmp) 2 ] that exhibits a monohapto coordination of the disulfide bridge in the dtbmp ligand with Ti−S bond lengths of 2.692(1) Å and 2.694(1) Å in the crystal.