Title
Complexation properties of N-thiophosphorylated thiourea <tex>$2-PyNHC(S)NHP(S)(OiPr)_{2}$</tex> towards <tex>$Ni^{II}$</tex>
Author
Faculty/Department
Faculty of Sciences. Physics
Publication type
article
Publication
London ,
Subject
Chemistry
Source (journal)
Journal of the Chemical Society: Dalton transactions. - London
Volume/pages
42(2013) :15 , p. 5252-5257
ISSN
0300-9246
1477-9226
1472-7773
ISI
000316300700008
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
Reaction of the deprotonated N-thiophosphorylated thiourea 2-PyNHC(S) NHP(S)(OiPr)(2) (HL) with NiCl2 leads to the complex [Ni{2-PyNHC(S) NP(S)(OiPr)(2)}(2)] ([NiL2]) with unprecedented 1,5,7-N, N', S-coordination of the ligand. Recrystallization of [NiL2] from a mixture of CH2Cl2-n-hexane or acetone-n-hexane leads to [Ni-(L-1,5,7-N, N', S)(2)]center dot CH2Cl2 and [Ni(L-1,5,7-N, N', S)(2)], respectively. The latter complex, in turn, shows a temperature-induced polymorphism. [NiL2] in solution shows a paramagnetic distorted octahedral structure where the metal center is coordinated through the nitrogen atoms of the phosphorylamide and pyridyl group functions, and oxygen atoms of the phosphorylamide unit. Furthermore, in the solid state at low temperature, [Ni(L-1,5,7-N, N', S)(2)] is shown from high-frequency EPR measurements to possess an S = 1 ground state with large anisotropy.
E-info
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