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Synthesis of Symmetric and Nonsymmetric Ni II Thiophosphinito PECSP (E = S, O) Pincer Complexes and Their Applications in Kumada Coupling under Mild Conditions
Author(s) -
Hasche Patrick,
Joksch Markus,
Vlachopoulou Georgia,
Agarwala Hemlata,
Spannenberg Anke,
Beweries Torsten
Publication year - 2018
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/ejic.201701442
Subject(s) - chemistry , pincer movement , pincer ligand , ligand (biochemistry) , medicinal chemistry , halide , aryl , catalysis , bromide , coupling reaction , stereochemistry , inorganic chemistry , organic chemistry , biochemistry , alkyl , receptor
The reaction of 1,3‐dimercaptobenzene with i Pr 2 PCl in the presence of the base NaH, furnishes the symmetric ligand [C 6 H 4 ‐1,3‐(SP i Pr 2 ) 2 ] ( 1a ). The direct reaction of this ligand as well as of the literature‐known nonsymmetric ligand [C 6 H 4 ‐1‐(SP i Pr 2 )‐3‐(OP i Pr 2 )] ( 1b ) with NiCl 2 affords the symmetric bis(thiophosphinito) PSCSP pincer complex [{C 6 H 3 ‐2,6‐(SP i Pr 2 ) 2 }NiCl] ( 2a ) as well as the phosphinito–thiophosphinito POCSP pincer complex [{C 6 H 3 ‐2‐(SP i Pr 2 )‐6‐(OP i Pr 2 )}NiCl] ( 2b ). Both complexes were fully characterised and their catalytic performance in Kumada coupling of aryl halides and p ‐tolylmagnesium bromide under mild conditions was evaluated.