02357nas a2200157   4500008004100000245013100041210006900172260000800241300001800249490000700267520171600274100002001990700002002010700003102030856013802061       2007                        eng d00aHighly air-stable anionic mononuclear and neutral binuclear palladium(ii) complexes for C−C and C−N bond-forming reactions0 aHighly airstable anionic mononuclear and neutral binuclear palla  cNOV  a11316–113270 v463 a<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‘-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 × 105 in the case of the Suzuki−Miyaura reaction).</p>1 aPunji, Benudhar1 aMague, Joel, T.1 aBalakrishna, Maravanji, S.  uhttp://library.ncl.res.in/content/highly-air-stable-anionic-mononuclear-and-neutral-binuclear-palladiumii-complexes-c%E2%88%92c-and-c01389nas a2200157   4500008004100000245009900041210006900140260000800209300001600217490000700233520079900240100002001039700002101059700002201080856012901102       2010                        eng d00aHighly stable adamantyl-substituted pincer-ligated iridium catalyst for alkane dehydrogenation0 aHighly stable adamantylsubstituted pincerligated iridium catalys  cMAY  a2702–27090 v293 a<p>The adamantyl-substituted pincer-ligand precursor AdPCP-H [(AdPCP = κ3-C6H3-2,6-(CH2PAd2)2); Ad = 1-adamantyl] has been synthesized by the reaction of 1,3-dibromoxylene with di-1-adamantylphosphine in the presence of triethylamine. Treatment of AdPCP-H with [Ir(COD)Cl]2 (COD = 1,5-cyclooctadiene) affords the pincer-ligated complex (AdPCP)IrHCl, which was crystallographically characterized. Dehydrohalogenation of (AdPCP)IrHCl either with LiBEt3H or with KOtBu, under hydrogen atmosphere, yields the hydrides (AdPCP)IrH2 and (AdPCP)IrH4. (AdPCP)IrH2 catalyzes dehydrogenation of alkanes with a level of activity comparable to that of the previously reported (tBuPCP)IrH2, while it is thermally much more robust than the tBuPCP analogue, as well as iPrPCP or tBuPOCOP pincer complexes.</p>1 aPunji, Benudhar1 aEmge, Thomas, J.1 aGoldman, Alan, S.  uhttp://library.ncl.res.in/content/highly-stable-adamantyl-substituted-pincer-ligated-iridium-catalyst-alkane-dehydrogenation