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Thio‐Ligation to Vanadium: The NSSN and S′N′O Donor Sets (N = Pyridine, N′ = Enamine; S = Thioether, S′ = Thiolate)
Author(s) -
Farahbakhsh Mahin,
Nekola Henning,
Schmidt Häke,
Rehder Dieter
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300815
Subject(s) - chemistry , thioether , schiff base , enamine , vanadium , deprotonation , medicinal chemistry , pyridine , imine , tautomer , ligand (biochemistry) , stereochemistry , thio , octahedron , sulfoxide , crystallography , crystal structure , catalysis , inorganic chemistry , organic chemistry , biochemistry , receptor , ion
The tetradentate, neutral disulfide [bis(thioether)] ligand 1,6‐bis( o ‐pyridyl)‐2,4‐dithiahexane, NSSN , reacts with [VCI 2 (tmeda) 2 ] to form the octahedral (all‐ cis ; C 2v ‐symmetric) complex [VCl 2 ( NSSN )] 1 , the first low‐valent vanadium complex in which the thio functions are exclusively organic sulfides. Treatment of (VOCl 2 (thf) 2 ] with O ‐mercaptoaniline, followed by reaction with o ‐hydroxynaphthaldehyde yields the non‐oxo V′” complex [V(S′N′O) 2 ] 2 , derived from the Schiff base HS′N′OH, where 0 and S′ are phenolate and thiophenolate functions, respectively, and N′ is the Schiff base (enamine) nitrogen. Complex 2 , with the ligands in a distorted trigonal‐antiprismatic array, is a rare example of a structurally characterized complex where the Schiff base is preserved at the expense of its thiazoline tautomeric form.