Organic soluble 56-membered copper(I) siloxane cage compound Cu(24)O(24)Si(8)R(8) (1, R = (2,6-iPr(2)C(6)H(3))N(SiMe(3))) has been synthesized and structurally characterized. It consists of a copper silica-supported structure, in which the metal ions are two-coordinate and covalently anchored onto the cage surface and the weak metal...metal d(10)-d(10) interactions are widely full within the cage, that is active in catalyzing the Ullmann-Goldberg-type C-N coupling reaction involving aryl or 2-thienyl bromides with heterocyclic nitrogen nucleophiles. This work provides insight into homogeneous catalysis utilizing the heterogeneous structure.
This paper reports the reactions of a monomeric aluminum dihydride LAlH2 (L = HC[C(Me)N(Ar)](2), Ar = 2,6-i-Pr2C6H3) with diazo, azido, and terminal alkyne compounds. The reaction of LAlH2 with N2CH(SiMe3) and N-3(1-Ad) occurred through an Al-H addition to end-on nitrogen to yield respective compounds LAl[N(H)N = CH(SiMe3)](2) (1) and LAl[N(H)N=N(1-Ad)](2) (2), while the reaction of LAlH2 with PhCa parts per thousand CH occurred through a stepwise deprotonation to yield LAlH(Ca parts per thousand CPh) (5) and LAl-(Ca parts per thousand CPh)(2) (6), respectively. 2 further reacted by N-2-release to yield LAl[NH(1-Ad)][N(H)N=N(1-Ad)] (3) and LAl[NH-(1-Ad)](2) (4) upon the increased temperature treatment. Compounds 1-6 have been fully characterized, revealing novel reactivity patterns of LAlH2 toward different substrates under the steric influence from the bulky L ligand at Al.National Natural Science Foundation of China [20842006, 20972129, 20902112]; China Postdoctoral Science Foundation [20090460748]; Fund for New Teacher of Higher Education [200803841012]; SRF for ROCS, SEM [2009060011500466
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