The local structures of rhodium complexes derived from the immobilization of Wilkinson’s complex, RhCl(PPh₃)₃, on SBA-15 silica functionalized with primary–amine, secondary–amine, or diphenylphosphine groups within the mesoporous channels were characterized by a series of techniques including XRD, HR-TEM, multinuclear (¹³C/²⁹Si/³¹P) solid-state NMR, 2D ³¹P{¹H} HETCOR NMR, XPS, and Rh K-edge EXAFS. Immobilization of RhCl(PPh₃)₃ through covalent bond formation with different functional groups grafted to the silica surface lead to variations in the local structure of the Rh center that has important implications for catalysis. The immobilized Rh complexes demonstrated high activity for the addition of alkynes with thiols (hydrothiolation) or sulfonic acids (hydrosulfonation) with excellent regio- and stereoselectivity under mild reaction conditions. This work demonstrates the elucidation of the local structure of the immobilized Rh complexes requires a complimentary multi-technique characterization approach that probes both the metal center itself and surrounding ligands.

威尔金森配合物RhCl（PPh ₃）₃固定在介孔通道内经伯胺，仲胺或二苯基膦基官能化的SBA-15二氧化硅上的铑配合物的局部结构已通过一系列技术进行了表征包括XRD，HR-TEM，多核（¹³ C / ²⁹ Si / ³¹ P）固态NMR，2D ³¹ P { ¹ H} HETCOR NMR，XPS和Rh K- edge EXAFS。RhCl（PPh ₃）_3的固定化通过与接枝到二氧化硅表面的不同官能团形成共价键会导致Rh中心局部结构发生变化，这对催化具有重要意义。固定化的Rh络合物在温和的反应条件下，对具有炔基和立体选择性的硫醇（氢巯基化）或磺酸（氢磺化）添加炔烃表现出很高的活性。这项工作表明固定化Rh复合物的局部结构的阐明需要一种互补的多技术表征方法，该方法可以探测金属中心本身和周围的配体。