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- Title
Solvent-Dependent Reversible.
- Authors
Ghisolfi, Alessio; Fliedel, Christophe; Rosa, Vitor; Pattacini, Roberto; Thibon, Aurore; Yu. Monakhov, Kirill; Braunstein, Pierre
- Abstract
The coordination chemistry of the DPPA-type functional phosphine bis(diphenylphosphino)( N-thioether)amine N(PPh2)2(CH2)3SMe ( 1) and its monosulfide derivative, (Ph2P)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), [NiCl2((Ph2P)N{P(S)Ph2}(CH2)3SMe- P,S)] ( 3), [Ni((Ph2P)N{P(S)Ph2}(CH2)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 [NiCl2LL′] and the paramagnetic ion-pair [Ni(LL′)2][NiCl4]. 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.
- Subjects
CHELATES; LIGAND exchange reactions; CRYSTAL structure; NUCLEAR magnetic resonance; FOURIER transform infrared spectroscopy
- Publication
Chemistry - An Asian Journal, 2013, Vol 8, Issue 8, p1795
- ISSN
1861-4728
- Publication type
Article
- DOI
10.1002/asia.201300687