Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/95052
Title: Synthesis and coordination chemistry of a 14-membered macrocyclic ligand containing one phosphorus, two sulfur and one ambidentate sulfoxide donor sets
Authors: Leung, P.-H. 
Liu, A.
Mok, K.F. 
White, A.J.P.
Williams, D.J.
Issue Date: 21-Apr-1999
Source: Leung, P.-H.,Liu, A.,Mok, K.F.,White, A.J.P.,Williams, D.J. (1999-04-21). Synthesis and coordination chemistry of a 14-membered macrocyclic ligand containing one phosphorus, two sulfur and one ambidentate sulfoxide donor sets. Journal of the Chemical Society - Dalton Transactions (8) : 1277-1282. ScholarBank@NUS Repository.
Abstract: The macrocyclic ligand PhP(CH2CH2SCH2CH2CH 2)2SO (L) was obtained from the reaction between bis(3-chloropropyl) sulfoxide and bis(2-mercaptoethyl)phenylphosphine in the presence of caesium carbonate. The ligand is stable in the solid state but rearranges slowly into the isomeric phosphine oxide S(CH2CH2CH2SCH2CH2) 2P(O)Ph in solution. In the presence of molecular iodine, the oxygen migration process occurred spontaneously and the phosphine oxide was obtained quantitatively within several minutes. When treated with [MCl2(CH3CN)2] (where M = Pd, Pt), the sulfinyl-substituted macrocycle functions as a bidentate ligand via its phosphorus and one of the thioether sulfur donor atoms giving the corresponding neutral square-planar complexes cis-[M(L-P,S)Cl2]. In both complexes, the sulfoxide group is not involved in metal complexation. However, when the dichloro complexes were treated with silver perchlorate, the corresponding tetradentate complexes [M{L-P,S,S,S}][ClO4]2 were formed. In both the perchlorate salts, the ambidentate sulfoxide functions are coordinated to the metal centre via their sulfur donor. In contrast to the previously reported acyclic analogues, the sulfoxide-metal bonds are kinetically stable.
Source Title: Journal of the Chemical Society - Dalton Transactions
URI: http://scholarbank.nus.edu.sg/handle/10635/95052
ISSN: 03009246
Appears in Collections:Staff Publications

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