@article {42755,
	title = {Highly air-stable anionic mononuclear and neutral binuclear palladium(ii) complexes for C-C and C-N bond-forming reactions},
	journal = {Inorganic Chemistry},
	volume = {46},
	year = {2007},
	month = {NOV},
	pages = {11316{\textendash}11327},
	type = {Article},
	abstract = {<p>The short-bite aminobis(phosphonite), PhN{P(-OC10H6(μ-S)C10H6O-)}2 (2), containing a mesocyclic thioether backbone is synthesized by either treating PhN(PCl2)2 with 2 equiv of thiobis(2,2{\textquoteleft}-naphthol) or reacting chlorophosphite (-OC10H6(μ-S)C10H6O-)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(-OC10H6(μ-S)C10H6O-)(O)-κP,κS}2] (3), whereas the same reaction with 2 equiv of Pd(COD)Cl2 in the presence of H2O and Et3N produces the mononuclear anionic complex [{(-OC10H6(μ-S)C10H6O-)P(O)-κP,κS}PdCl2](Et3NH) (5). By contrast, reaction of 2 with 2 equiv of Pd(COD)Cl2 and H2O in the absence of Et3N gives the hydrogen phosphonate coordinated complex [{(-OC10H6(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(-OC10H6(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 {\texttimes} 105 in the case of the Suzuki-Miyaura reaction).</p>},
	doi = {10.1021/ic701674x},
	author = {Punji, Benudhar and Mague, Joel T. and Balakrishna, Maravanji S.}
}
