TY - JOUR
T1 - Solvent-dependent reversible ligand exchange in nickel complexes of a monosulfide bis(diphenylphosphino)(N-thioether)amine
AU - Ghisolfi, Alessio
AU - Fliedel, Christophe
AU - Rosa, Vitor
AU - Pattacini, Roberto
AU - Thibon, Aurore
AU - Monakhov, Kirill Yu
AU - Braunstein, Pierre
PY - 2013/8/1
Y1 - 2013/8/1
N2 - The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)(N-thioether)amine N(PPh2)2(CH 2)3SMe (1) and its monosulfide derivative, (Ph 2P)N{P(S)Ph2}(CH2)3SMe (1×S), towards NiII precursors has been investigated. The crystal structures of N{P(S)Ph2}2(CH2)3SMe (1×S2), [NiCl2{(Ph2P) 2N(CH2)3SMe-P,P}] (2), [NiCl 2((Ph2P)N{P(S)Ph2}(CH2) 3SMe-P,S)] (3), [Ni((Ph2P)N{P(S)Ph2}(CH 2)3SMe-P,S)2]NiCl4 (3'), [Ni((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S) 2](BF4)2 (4), and [Ni((Ph2P)NH{P(S) Ph2}-P,S)2]Cl2 (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 NiII 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 2LL'] 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. Swap deal: Easy migration of a P,S-chelating ligand to form five-membered rings in NiII complexes accounts for the reversible ligand redistribution that occurs in the equilibrium between the neutral complex [NiCl2LL'] and the ion-pair [Ni(LL')2][NiCl4].
AB - The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)(N-thioether)amine N(PPh2)2(CH 2)3SMe (1) and its monosulfide derivative, (Ph 2P)N{P(S)Ph2}(CH2)3SMe (1×S), towards NiII precursors has been investigated. The crystal structures of N{P(S)Ph2}2(CH2)3SMe (1×S2), [NiCl2{(Ph2P) 2N(CH2)3SMe-P,P}] (2), [NiCl 2((Ph2P)N{P(S)Ph2}(CH2) 3SMe-P,S)] (3), [Ni((Ph2P)N{P(S)Ph2}(CH 2)3SMe-P,S)2]NiCl4 (3'), [Ni((Ph2P)N{P(S)Ph2}(CH2)3SMe-P,S) 2](BF4)2 (4), and [Ni((Ph2P)NH{P(S) Ph2}-P,S)2]Cl2 (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 NiII 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 2LL'] 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. Swap deal: Easy migration of a P,S-chelating ligand to form five-membered rings in NiII complexes accounts for the reversible ligand redistribution that occurs in the equilibrium between the neutral complex [NiCl2LL'] and the ion-pair [Ni(LL')2][NiCl4].
KW - chelates
KW - ligand exchange
KW - nickel
KW - short-bite ligands
KW - solvent effects
UR - http://www.scopus.com/inward/record.url?scp=84881150838&partnerID=8YFLogxK
U2 - 10.1002/asia.201300687
DO - 10.1002/asia.201300687
M3 - Article
C2 - 23794386
AN - SCOPUS:84881150838
SN - 1861-4728
VL - 8
SP - 1795
EP - 1805
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
IS - 8
ER -