Jarupatrakorn Jonggol, Tilley T Don
Department of Chemsitry, University of California, Berkeley, CA 94720-1460, USA.
Dalton Trans. 2004 Sep 7(17):2808-13. doi: 10.1039/B407398C. Epub 2004 Aug 3.
Reaction of [(diene)RhCl]2 with 2 equiv of KOSi(OtBu)3 afforded [(diene)Rh[mu-OSi(OtBu)3]]2, where diene=cod (1) and nbd (2). Multinuclear NMR studies reveal that 1 and 2 have a dimeric structure with bridging tris(tert-butoxy)siloxy ligands. These dimers are folded along the O...O axis. Complexes and reacted with PR3(R=Me, Ph) to give monomeric products, the formulae of which depend on the amount of PR3 added ((diene)RhOSi(OtBu)3 and RhOSi(OtBu)33). The behavior of 1 towards water and methanol is discussed. Thermogravimetric analyses (TGAs) of 1 and 2 reveal rather sharp conversions to rhodium-containing materials. Thermolysis of 1 in toluene at 180 degrees C resulted in formation of a black precipitate, which contained rhodium nanoparticles with an average diameter of 22 nm, as determined by powder X-ray diffraction (PXRD), after calcination at 300 degrees C for 1 h.
[(二烯基)RhCl]₂ 与 2 当量的 KOSi(OtBu)₃ 反应生成 [(二烯基)Rh[μ - OSi(OtBu)₃]]₂，其中二烯基 = cod (1) 和 nbd (2)。多核核磁共振研究表明，1 和 2 具有由桥联三(叔丁氧基)硅氧基配体构成的二聚体结构。这些二聚体沿 O...O 轴折叠。配合物与 PR₃（R = Me、Ph）反应生成单体产物，其化学式取决于所加 PR₃ 的量（(二烯基)RhOSi(OtBu)₃ 和 RhOSi(OtBu)₃₃）。讨论了 1 与水和甲醇的反应行为。对 1 和 2 的热重分析（TGA）显示向含铑材料的转变相当明显。1 在甲苯中于 180℃ 热解生成黑色沉淀，经粉末 X 射线衍射（PXRD）测定，在 300℃ 煅烧 1 小时后，该沉淀含有平均直径为 22 nm 的铑纳米颗粒。
