Structural elucidation of supported Rh complexes derived from RhCl(PPh3)3 immobilized on surface-functionalized SBA-15 and their catalytic performance for C-heteroatom (S, O) bond formation

Yong Yang, Ji Wong Chang, Robert Martin Rioux, Jr.

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2 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)43-54
Number of pages12
JournalJournal of Catalysis
Volume365
DOIs
StatePublished - Sep 1 2018

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immobilization
Silicon Dioxide
Silica
Nuclear magnetic resonance
silicon dioxide
Stereoselectivity
Regioselectivity
Rhodium
nuclear magnetic resonance
Covalent bonds
Alkynes
Sulfonic Acids
sulfonic acid
covalent bonds
alkynes
rhodium
Sulfhydryl Compounds
thiols
Functional groups
Catalysis

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

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title = "Structural elucidation of supported Rh complexes derived from RhCl(PPh3)3 immobilized on surface-functionalized SBA-15 and their catalytic performance for C-heteroatom (S, O) bond formation",
abstract = "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.",
author = "Yong Yang and Chang, {Ji Wong} and {Rioux, Jr.}, {Robert Martin}",
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T1 - Structural elucidation of supported Rh complexes derived from RhCl(PPh3)3 immobilized on surface-functionalized SBA-15 and their catalytic performance for C-heteroatom (S, O) bond formation

AU - Yang, Yong

AU - Chang, Ji Wong

AU - Rioux, Jr., Robert Martin

PY - 2018/9/1

Y1 - 2018/9/1

N2 - 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.

AB - 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.

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