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Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC10H6(mu-S)C10H6O-]PNC4H8E (E = O, NMe)

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Title Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC10H6(mu-S)C10H6O-]PNC4H8E (E = O, NMe)
 
Creator PUNJI, B
MAGUE, JT
BALAKRISHNA, MS
 
Subject cross-coupling reactions
allylic substitution-reactions
pauson-khand reaction
sulfur donor action
coordination chemistry
molecular-structures
palladium complex
structural-characterization
asymmetric hydrogenation
reversible conversion
thioether-aminophosphonites
ps ligands copper
gold
 
Description Group 11 metal complexes of the mesocyclic thioether aminophosphonites [-OC10H6(mu-S)C10H6O-]PNC4H8E {2a: E = O; 2b: E = NMe; IUPAC names: 4-(dinaphtho[2,1-d:1',2'-g][1,3,6,2]dioxathiaphosphocin-4-yl)morpholine (2a), 1-(dinaphtho[2,1-d:1',2'-gl[1,3,6,2]dioxathiaphosphocin-4-yl)- 4-methylpiperazine (2b)} are reported. Thioether aminophosphonites 2a and 2b react with CuX (X = Cl, Br, and I) in a 1:1 molar ratio to give the tricoordinate, dimeric complexes [{[{-OC10H6(mu-S)C10H6O-}PNC4H8E-kappa P]Cu(mu-X)}(2)] (4a: E = O, X = Cl; 4b: E NMe, X = Cl; 5a: E = O, X = Br; 5b: E = NMe, X = Br; 6a: E = O, X = I; 6b: E = NMe, X = I), whereas with 2:1 molar ratios monomeric complexes of the type [{[-OC10H6(mu-S)C10H6O-]PNC4H8O-kappa P)(2)CUX] (7a: E = O, X = Cl; 7b: E = NMe, X = Cl; 8a: E = O, X = Br; 8b: E = NMe, X = Br; 9a: E = O, X = I; 9b: E = NMe, X = I) are obtained in excellent yield. The PS-chelated cationic complexes [{[-OC10H6(mu-S)C10H6O-]PNC4H8E-kappa P,kappa S](2)Cu]BF4 (10a: E = O; 10b: E = We) are obtained when 2a and 2b are treated with half an equivalent of [(MeCN)(4)Cu]BF4. Similarly, the silver complexes [{[{-OC10H6(mu-S)C10H6O-}PNC4H8E-kappa P,kappa S]-AgCF3SO3}(2)] (11a: E = O: 11b: E = NMe) and [{[-OC10H6(mu-S)C10H6O-]PNC4H8E-kappa P,kappa S)Ag(PPh3)]CF3SO3 (12a: E = O; 12b: E = NMe) are synthesized by the treatment of thioether aminophosphonites 2a and 2b with AgOTf and [Ag(PPh3)][OTf], respectively. Reactions of 2a and 2b with [AuCl(SMe2)] produce the simple monomeric gold(I) complexes [{[-OC10H6(mu-S)C10H6O-]PNC4H8E-kappa P)AuCl] (13a: E = O; 13b: E = NMe). The iodo derivatives [{[-OC10H6(mu-S)C10H6O-]PNC4H8E-kappa P)AuI] (14a: E = O; 14b: E = NMe) are obtained by the halide-exchange reaction of 13a and 13b with CuI at room temperature. The structures of complexes 5a, 7a, 8a, 13a, 13b, and 14a are confirmed by single-crystal X-ray diffraction studies. In all of these complexes, the sulfur atom in the mesocyclic ring shows coordinative interaction towards the phosphorus atom, and in 5a, 7a, 8a, and 14a towards the metal center as well.
 
Publisher WILEY-V C H VERLAG GMBH
 
Date 2011-09-01T17:08:44Z
2011-12-26T12:59:44Z
2011-12-27T05:52:30Z
2011-09-01T17:08:44Z
2011-12-26T12:59:44Z
2011-12-27T05:52:30Z
2007
 
Type Article
 
Identifier EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (5), 720-731
1434-1948
http://dx.doi.org/10.1002/ejic.200600913
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12828
http://hdl.handle.net/10054/12828
 
Language en