Attempts to optimise the synthesis of a new class of nickel(II) dithiolene complexes starting from 1,3-dialkylimidazolidine-2-thione-4,5-dione (1) and Lawesson's reagent (2) have afforded a new and easy one-step synthesis of phosphonodithioate nickel(II) complexes. This consists of the direct reaction between NiCl2 and Lawesson's reagent in the appropriate alcohol R′OH (R=Me, Et, i-Pr, Bu, Bz) as solvent, to give the bis-[O-alkyl/aryl-(4-methoxyphenyl)phosphonodithioato] nickel(II) complexes (5a-e) with high yields (64-91%). Among them, trans-bis-[O-ethyl-(4-methoxyphenyl)phosphonodithioato] nickel(II) (5b) was characterised by means of X-ray diffraction measurements on a single crystal. The compound crystallises in the triclinic, P1̄ space group with a=6.4840(7), b=7.6032(9), c=13.055(2) Å, α=99.481(9), β=99.43(1), γ=104.487(9)° and Z=1. The compound is centrosymmetric and exhibits discrete monomeric units with the ligand acting as S,S-bidentate. To explain the reactivity of Lawesson's reagent, the formation of 4-methoxyphenyldithiophosphorane (6) as intermediate has been suggested. The reaction was also tested for Pd(II) and Pt(II), but in these cases the yields were not as satisfactory as for Ni(II).
New perspectives in phosphonodithioate coordination chemistry. Synthesis and X-ray crystal structure of trans-bis-[O-ethyl-(4-methoxyphenyl)phosphonodithioato] nickel(II)
ARCA, MASSIMILIANO;ISAIA, FRANCESCO;LIPPOLIS, VITO;
1997-01-01
Abstract
Attempts to optimise the synthesis of a new class of nickel(II) dithiolene complexes starting from 1,3-dialkylimidazolidine-2-thione-4,5-dione (1) and Lawesson's reagent (2) have afforded a new and easy one-step synthesis of phosphonodithioate nickel(II) complexes. This consists of the direct reaction between NiCl2 and Lawesson's reagent in the appropriate alcohol R′OH (R=Me, Et, i-Pr, Bu, Bz) as solvent, to give the bis-[O-alkyl/aryl-(4-methoxyphenyl)phosphonodithioato] nickel(II) complexes (5a-e) with high yields (64-91%). Among them, trans-bis-[O-ethyl-(4-methoxyphenyl)phosphonodithioato] nickel(II) (5b) was characterised by means of X-ray diffraction measurements on a single crystal. The compound crystallises in the triclinic, P1̄ space group with a=6.4840(7), b=7.6032(9), c=13.055(2) Å, α=99.481(9), β=99.43(1), γ=104.487(9)° and Z=1. The compound is centrosymmetric and exhibits discrete monomeric units with the ligand acting as S,S-bidentate. To explain the reactivity of Lawesson's reagent, the formation of 4-methoxyphenyldithiophosphorane (6) as intermediate has been suggested. The reaction was also tested for Pd(II) and Pt(II), but in these cases the yields were not as satisfactory as for Ni(II).I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.