Surface Organometallic Chemistry on Oxides: Reaction of Trimethylphosphine with Bis(allyl)rhodium Grafted onto Silica

Susannah L. Scott; Pascal Dufour; Catherine C. Santini; Jean Marie Basset

doi:10.1021/ic9405790

Surface Organometallic Chemistry on Oxides: Reaction of Trimethylphosphine with Bis(allyl)rhodium Grafted onto Silica

Susannah L. Scott, Pascal Dufour, Catherine C. Santini, Jean Marie Basset^*

^*Corresponding author for this work

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

17 Scopus citations

Abstract

The reaction of Rh(η³-C₃H₅)₃ with the surface hydroxyl groups of partially dehydroxylated silica leads to the formation of the surface organometallic complex (≡SiO)(≡SiOX)Rh(η³-C₃H₅) ₂, 1 (where X is H or Si≡), with evolution of propene. The reaction of 1 with PMe₃ was examined, and two major pathways were discovered. Reductive elimination of two allyl ligands as 1,5-hexadiene and coordination of PMe₃ give the surface product (≡SiO)Rh(PMe₃)₃, 2, which was characterized by elemental analysis, IR and ³¹P MAS NMR spectroscopy. We also prepared 2 independently from CH₃Rh(PMe₃)₃ and partially dehydroxylated silica. The second major reaction pathway is the elimination of propene to give (≡SiO)₂Rh(η¹-C₃H ₅)(PMe₃)₃, 3. The presence of the σ-bound allyl ligand was inferred from its characteristic IR spectrum. The reactivity of 3 toward CO was examined: insertion of CO into the Rh-C bond followed by reductive elimination of the silyl ester =SiOC(O)C₃H₅ produces (≡SiO)Rh(CO)(PMe₃)₂, 4. In static vacuum, 3 decomposes to give allyl alcohol, which is slowly decarbonylated by 2.

Original language	English (US)
Pages (from-to)	869-875
Number of pages	7
Journal	Inorganic chemistry
Volume	35
Issue number	4
DOIs	https://doi.org/10.1021/ic9405790
State	Published - 1996
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{6b4e68426cf2417a8431bd5e38537fb6,

title = "Surface Organometallic Chemistry on Oxides: Reaction of Trimethylphosphine with Bis(allyl)rhodium Grafted onto Silica",

abstract = "The reaction of Rh(η3-C3H5)3 with the surface hydroxyl groups of partially dehydroxylated silica leads to the formation of the surface organometallic complex (≡SiO)(≡SiOX)Rh(η3-C3H5) 2, 1 (where X is H or Si≡), with evolution of propene. The reaction of 1 with PMe3 was examined, and two major pathways were discovered. Reductive elimination of two allyl ligands as 1,5-hexadiene and coordination of PMe3 give the surface product (≡SiO)Rh(PMe3)3, 2, which was characterized by elemental analysis, IR and 31P MAS NMR spectroscopy. We also prepared 2 independently from CH3Rh(PMe3)3 and partially dehydroxylated silica. The second major reaction pathway is the elimination of propene to give (≡SiO)2Rh(η1-C3H 5)(PMe3)3, 3. The presence of the σ-bound allyl ligand was inferred from its characteristic IR spectrum. The reactivity of 3 toward CO was examined: insertion of CO into the Rh-C bond followed by reductive elimination of the silyl ester =SiOC(O)C3H5 produces (≡SiO)Rh(CO)(PMe3)2, 4. In static vacuum, 3 decomposes to give allyl alcohol, which is slowly decarbonylated by 2.",

author = "Scott, {Susannah L.} and Pascal Dufour and Santini, {Catherine C.} and Basset, {Jean Marie}",

year = "1996",

doi = "10.1021/ic9405790",

language = "English (US)",

volume = "35",

pages = "869--875",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Surface Organometallic Chemistry on Oxides

T2 - Reaction of Trimethylphosphine with Bis(allyl)rhodium Grafted onto Silica

AU - Scott, Susannah L.

AU - Dufour, Pascal

AU - Santini, Catherine C.

AU - Basset, Jean Marie

PY - 1996

Y1 - 1996

N2 - The reaction of Rh(η3-C3H5)3 with the surface hydroxyl groups of partially dehydroxylated silica leads to the formation of the surface organometallic complex (≡SiO)(≡SiOX)Rh(η3-C3H5) 2, 1 (where X is H or Si≡), with evolution of propene. The reaction of 1 with PMe3 was examined, and two major pathways were discovered. Reductive elimination of two allyl ligands as 1,5-hexadiene and coordination of PMe3 give the surface product (≡SiO)Rh(PMe3)3, 2, which was characterized by elemental analysis, IR and 31P MAS NMR spectroscopy. We also prepared 2 independently from CH3Rh(PMe3)3 and partially dehydroxylated silica. The second major reaction pathway is the elimination of propene to give (≡SiO)2Rh(η1-C3H 5)(PMe3)3, 3. The presence of the σ-bound allyl ligand was inferred from its characteristic IR spectrum. The reactivity of 3 toward CO was examined: insertion of CO into the Rh-C bond followed by reductive elimination of the silyl ester =SiOC(O)C3H5 produces (≡SiO)Rh(CO)(PMe3)2, 4. In static vacuum, 3 decomposes to give allyl alcohol, which is slowly decarbonylated by 2.

AB - The reaction of Rh(η3-C3H5)3 with the surface hydroxyl groups of partially dehydroxylated silica leads to the formation of the surface organometallic complex (≡SiO)(≡SiOX)Rh(η3-C3H5) 2, 1 (where X is H or Si≡), with evolution of propene. The reaction of 1 with PMe3 was examined, and two major pathways were discovered. Reductive elimination of two allyl ligands as 1,5-hexadiene and coordination of PMe3 give the surface product (≡SiO)Rh(PMe3)3, 2, which was characterized by elemental analysis, IR and 31P MAS NMR spectroscopy. We also prepared 2 independently from CH3Rh(PMe3)3 and partially dehydroxylated silica. The second major reaction pathway is the elimination of propene to give (≡SiO)2Rh(η1-C3H 5)(PMe3)3, 3. The presence of the σ-bound allyl ligand was inferred from its characteristic IR spectrum. The reactivity of 3 toward CO was examined: insertion of CO into the Rh-C bond followed by reductive elimination of the silyl ester =SiOC(O)C3H5 produces (≡SiO)Rh(CO)(PMe3)2, 4. In static vacuum, 3 decomposes to give allyl alcohol, which is slowly decarbonylated by 2.

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U2 - 10.1021/ic9405790

DO - 10.1021/ic9405790

M3 - Article

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JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 4

ER -

Surface Organometallic Chemistry on Oxides: Reaction of Trimethylphosphine with Bis(allyl)rhodium Grafted onto Silica

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