Premium
Ring‐Opening of Lawesson’s Reagent: New Syntheses of Phosphono‐ and Amidophosphono‐Dithioato Complexes − Structural and CP‐MAS 31 P‐NMR Characterization of [ p ‐CH 3 OPh(X)PS 2 ] 2 M (X = MeO, i PrNH; M = Ni II , Pd II , and Pt II )
Author(s) -
Aragoni M. Carla,
Arca Massimiliano,
Demartin Francesco,
Devillanova Francesco A.,
Graiff Claudia,
Isaia Francesco,
Lippolis Vito,
Tiripicchio Antonio,
Verani Gaetano
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200010)2000:10<2239::aid-ejic2239>3.0.co;2-0
Subject(s) - chemistry , reagent , ring (chemistry) , characterization (materials science) , stereochemistry , crystallography , organic chemistry , nanotechnology , materials science
The opening of the P 2 S 2 tetraatomic ring of Lawesson’s reagent ( 4 ) has proved versatile in synthesizing phosphono‐ and amidophosphono‐dithioato mononuclear complexes [ p ‐CH 3 OPh(X)PS 2 ] 2 M [X = CH 3 O, i PrNH; M = Ni II , Pd II , Pt II ]. A one‐step reaction of 4 with the appropriate metal salt in CH 3 OH, or in the presence of a stoichiometric amount of i PrNH 2 in CHCl 3 , is used in the direct synthesis of the Ni II and Pd II complexes, but does not work in the Pt II complexes. Alternatively, these syntheses can be carried out: i) by preparation and isolation of O ‐methyl(4‐methoxyphenyl)phosphonodithioate ( 6 ) salts or isopropylamido(4‐methoxyphenyl)‐ phosphonodithioate ( 7 ) salts by treating 4 with CH 3 O − in CH 3 OH or with i PrNH 2 , respectively; ii) by reaction of 6 or 7 with MCl 2 or K 2 MCl 4 [M = Ni II , Pd II , Pt II ] to give trans ‐bis[ O ‐methyl(4‐methoxyphenyl)phosphonodithioato]M and trans ‐bis[isopropylamido(4‐methoxyphenyl)phosphonodithioato]M complexes. Following these routes, trans ‐bis[ O ‐methyl(4‐methoxyphenyl)phosphonodithioato]M [M = Ni ( 8a ), Pd ( 8b ), and Pt ( 8c )] and trans ‐bis[isopropylamido(4‐methoxyphenyl)phosphonodithioato]M [M = Ni ( 9a ), Pd ( 9b ), and Pt ( 9c )] complexes have been synthesized and fully characterized by FAB mass, FT‐IR, FT‐Raman, UV/Vis, and CP‐MAS 31 P‐NMR spectroscopy; the crystal structures of 7 , 8b , 8c , and 9a are also reported.