1001201-67-7Relevant academic research and scientific papers
Highly air-stable anionic mononuclear and neutral binuclear palladium(II) complexes for C-C and C-N bond-forming reactions
Punji, Benudhar,Mague, Joel T.,Balakrishna, Maravanji S.
, p. 11316 - 11327 (2007)
The short-bite aminobis(phosphonite), PhN{P(-OC10H 6(μ-S)C10H6O-)}2 (2), containing a mesocyclic thioether backbone is synthesized by either treating PhN(PCl 2)2 with 2 equiv of thiobis(2,2′-naphthol) or reacting chlorophosphite (-OC10H6(μ-S)C 10H6O-)PCl (1) with aniline in the presence of a base. Treatment of 2 with an equimolar amount of Pd(COD)Cl2 in the presence of H2O affords a P-N-P-bridged and P,S-metalated binuclear complex, [PhN(P(-OC10H6(μ-S)C10H6O-)- κP)2Pd2Cl2{P(-OC10H 6(μ-S)C10H6O-)(O)-κP,κS} 2] (3), whereas the same reaction with 2 equiv of Pd(COD)Cl 2 in the presence of H2O and Et3N produces the mononuclear anionic complex [{(-OC10H6-(μ-S)C 10H6O-)P(O)-κP,κS}PdCl2](Et 3NH) (5). By contrast, reaction of 2 with 2 equiv of Pd(COD)Cl 2 and H2O in the absence of Et3N gives the hydrogen phosphonate coordinated complex [{(-OC10H 6(μ-S)C10H6O-)P(OH)}-PdCl2] (4) which converts to the anionic complex in solution or in the presence of a base. Compound 2 on treatment with Pt(COD)X2 (X = Cl or I) afforded P-coordinated four-membered chelate complexes [PhN(P(-OC10H 6(μ-S)-C10H6O-)-κP) 2PtX2] (6 X = Cl, 7 X = I). The crystal structures of compounds 2, 3, 5, and 7 are reported. Compound 3 is the first example of a crystallographically characterized binuclear palladium complex containing a bidentate bridging ligand and its hydrolyzed fragments forming metallacycles containing a palladium-phosphorus σ bond. All palladium complexes proved to be very good catalysts for the Suzuki-Miyaura and Mizoroki-Heck cross-coupling and amination reactions with excellent turnover numbers (TON up to 1.46 × 105 in the case of the Suzuki-Miyaura reaction).
