Silica-supported rhodium hydrides stabilized by triisopropylphosphine

Susannah L. Scott; Allison Mills; Chhor Chao; Jean Marie Basset; Nicolas Millot; Catherine C. Santini

doi:10.1016/S1381-1169(03)00327-3

Silica-supported rhodium hydrides stabilized by triisopropylphosphine

Susannah L. Scott^*, Allison Mills, Chhor Chao, Jean Marie Basset, Nicolas Millot, Catherine C. Santini

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

The reaction of the silica-supported complex (≡SiO)(≡ SiOX)Rh(η³-C₃H₅)₂, where X is H or Si, with excess PⁱPr₃ leads to the formation of the chemisorbed bis(phosphine) Rh(I) complex [≡SiORh(PⁱPr ₃)₂]_x, proposed to be dimeric (x = 2) on the basis of the ³¹P MAS NMR spectrum. The phosphine complex irreversibly binds H₂ to give a hydride complex, ≡SiORh(P ⁱPr₃)₂(H)₂, characterized by IR and ³¹P MAS NMR spectroscopy as well as D-exchange. The coordinatively unsaturated hydride complex is inferred to be the active site for hydrogenation of olefins under mild conditions.

Original language	English (US)
Pages (from-to)	457-463
Number of pages	7
Journal	Journal of Molecular Catalysis A: Chemical
Volume	204-205
DOIs	https://doi.org/10.1016/S1381-1169(03)00327-3
State	Published - Sep 15 2003
Externally published	Yes

Keywords

Catalysis
Olefin hydrogenation
Silica
Surface organometallic chemistry

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

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10.1016/S1381-1169(03)00327-3

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title = "Silica-supported rhodium hydrides stabilized by triisopropylphosphine",

abstract = "The reaction of the silica-supported complex (≡SiO)(≡ SiOX)Rh(η3-C3H5)2, where X is H or Si, with excess PiPr3 leads to the formation of the chemisorbed bis(phosphine) Rh(I) complex [≡SiORh(PiPr 3)2]x, proposed to be dimeric (x = 2) on the basis of the 31P MAS NMR spectrum. The phosphine complex irreversibly binds H2 to give a hydride complex, ≡SiORh(P iPr3)2(H)2, characterized by IR and 31P MAS NMR spectroscopy as well as D-exchange. The coordinatively unsaturated hydride complex is inferred to be the active site for hydrogenation of olefins under mild conditions.",

keywords = "Catalysis, Olefin hydrogenation, Silica, Surface organometallic chemistry",

author = "Scott, {Susannah L.} and Allison Mills and Chhor Chao and Basset, {Jean Marie} and Nicolas Millot and Santini, {Catherine C.}",

year = "2003",

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doi = "10.1016/S1381-1169(03)00327-3",

language = "English (US)",

volume = "204-205",

pages = "457--463",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Silica-supported rhodium hydrides stabilized by triisopropylphosphine

AU - Scott, Susannah L.

AU - Mills, Allison

AU - Chao, Chhor

AU - Basset, Jean Marie

AU - Millot, Nicolas

AU - Santini, Catherine C.

PY - 2003/9/15

Y1 - 2003/9/15

N2 - The reaction of the silica-supported complex (≡SiO)(≡ SiOX)Rh(η3-C3H5)2, where X is H or Si, with excess PiPr3 leads to the formation of the chemisorbed bis(phosphine) Rh(I) complex [≡SiORh(PiPr 3)2]x, proposed to be dimeric (x = 2) on the basis of the 31P MAS NMR spectrum. The phosphine complex irreversibly binds H2 to give a hydride complex, ≡SiORh(P iPr3)2(H)2, characterized by IR and 31P MAS NMR spectroscopy as well as D-exchange. The coordinatively unsaturated hydride complex is inferred to be the active site for hydrogenation of olefins under mild conditions.

AB - The reaction of the silica-supported complex (≡SiO)(≡ SiOX)Rh(η3-C3H5)2, where X is H or Si, with excess PiPr3 leads to the formation of the chemisorbed bis(phosphine) Rh(I) complex [≡SiORh(PiPr 3)2]x, proposed to be dimeric (x = 2) on the basis of the 31P MAS NMR spectrum. The phosphine complex irreversibly binds H2 to give a hydride complex, ≡SiORh(P iPr3)2(H)2, characterized by IR and 31P MAS NMR spectroscopy as well as D-exchange. The coordinatively unsaturated hydride complex is inferred to be the active site for hydrogenation of olefins under mild conditions.

KW - Catalysis

KW - Olefin hydrogenation

KW - Silica

KW - Surface organometallic chemistry

UR - http://www.scopus.com/inward/record.url?scp=0041836338&partnerID=8YFLogxK

U2 - 10.1016/S1381-1169(03)00327-3

DO - 10.1016/S1381-1169(03)00327-3

M3 - Article

AN - SCOPUS:0041836338

SN - 1381-1169

VL - 204-205

SP - 457

EP - 463

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

ER -

Silica-supported rhodium hydrides stabilized by triisopropylphosphine

Abstract

Keywords

ASJC Scopus subject areas

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