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Solvent‐Dependent Reversible Ligand Exchange in Nickel Complexes of a Monosulfide Bis(diphenylphosphino)( N ‐thioether)amine
Author(s) -
Ghisolfi Alessio,
Fliedel Christophe,
Rosa Vitor,
Pattacini Roberto,
Thibon Aurore,
Yu. Monakhov Kirill,
Braunstein Pierre
Publication year - 2013
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201300687
Subject(s) - chemistry , thioether , ligand (biochemistry) , chelation , amine gas treating , phosphine , nickel , medicinal chemistry , crystal structure , crystallography , stereochemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry , receptor
Abstract The coordination chemistry of the DPPA‐type functional phosphine bis(diphenylphosphino)( N ‐thioether)amine N(PPh 2 ) 2 (CH 2 ) 3 SMe ( 1 ) and its monosulfide derivative, (Ph 2 P)N{P(S)Ph 2 }(CH 2 ) 3 SMe ( 1⋅S ), towards Ni II precursors has been investigated. The crystal structures of N{P(S)Ph 2 } 2 (CH 2 ) 3 SMe ( 1⋅S 2 ), [NiCl 2 {(Ph 2 P) 2 N(CH 2 ) 3 SMe‐ P,P }] ( 2 ), [NiCl 2 ((Ph 2 P)N{P(S)Ph 2 }(CH 2 ) 3 SMe‐ P,S )] ( 3 ), [Ni((Ph 2 P)N{P(S)Ph 2 }(CH 2 ) 3 SMe‐ P,S ) 2 ]NiCl 4 ( 3′ ), [Ni((Ph 2 P)N{P(S)Ph 2 }(CH 2 ) 3 SMe‐ P,S ) 2 ](BF 4 ) 2 ( 4 ), and [Ni((Ph 2 P)NH{P(S)Ph 2 }‐ P,S ) 2 ]Cl 2 ( 5 ) have been determined by single‐crystal X‐ray diffraction. In all of the complexes with the hybrid ligand 1⋅S , P,S‐chelation to the Ni II center is observed. Despite the stability generally associated with five‐membered ring chelation, easy migration of this LL′‐type P,S‐chelating ligand from one metal center to another was observed, which accounts for the reversible ligand‐redistribution reaction occurring in the equilibrium between the neutral, diamagnetic complex [NiCl 2 LL′] and the paramagnetic ion‐pair [Ni(LL′) 2 ][NiCl 4 ]. Detailed investigations by multinuclear NMR, UV/Vis, and FTIR spectroscopic methods and DFT calculations are reported. Each of the formula isomers 3 and 3′ can be selectively obtained, depending on the experimental conditions.