Rhodium complexes of PCNHCP: Oxidative addition of dichloromethane and catalytic hydrosilylation of alkynes affording (E)-alkenylsilanes

Jing Yao Zeng, Meng Hua Hsieh, Hon Man Lee

Research output: Contribution to journalArticle

84 Citations (Scopus)

Abstract

New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP) 2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the presumably formed nucleophilic RhI(PCNHCP)Cl intermediate (A), undergoes a C-Cl bond activation of CH2Cl2 giving cis,mer-Rh III(PCNHCP)(CH2Cl)Cl2 (3) as the final product. Attempts to isolate A affords the oxidative degradation product of mer-RhIII(PCNHCP)Cl3 complex (4). In contrast, the rhodium(I) center in Rh(PCNHCP)(CO)Cl (5) is stabilized by the π-back bonding of CO ligand; a robust complex is, therefore, obtained. The solid-state structures of 2 and 3 were determined by X-ray diffraction. Complexes 3-5 are catalyst precursors for efficient, chemoselective hydrosilylation of alkynes. For the reaction between phenylacetylene and dimethylphenylsilane, a rapid hydrosilylation occurs, producing isomers of alkenylsilanes; then a slow isomerization pathway converts (Z)-alkenylsilane to its (E)-isomer. For 3, under catalytic condition, a facile reductive elimination of dichloromethane giving A is anticipated. The similarity in reactivity and selectivity between 3, 4 and 5 suggests the involvement of A as the active species in a common catalytic cycle.

Original languageEnglish
Pages (from-to)5662-5671
Number of pages10
JournalJournal of Organometallic Chemistry
Volume690
Issue number24-25
DOIs
Publication statusPublished - 2005 Dec 1

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Hydrosilylation
Rhodium
Alkynes
Methylene Chloride
Dichloromethane
alkynes
Carbon Monoxide
rhodium
Isomers
isomers
crack opening displacement
products
Isomerization
Silver
X-Ray Diffraction
isomerization
reagents
elimination
reactivity
selectivity

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "Rhodium complexes of PCNHCP: Oxidative addition of dichloromethane and catalytic hydrosilylation of alkynes affording (E)-alkenylsilanes",
abstract = "New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP) 2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the presumably formed nucleophilic RhI(PCNHCP)Cl intermediate (A), undergoes a C-Cl bond activation of CH2Cl2 giving cis,mer-Rh III(PCNHCP)(CH2Cl)Cl2 (3) as the final product. Attempts to isolate A affords the oxidative degradation product of mer-RhIII(PCNHCP)Cl3 complex (4). In contrast, the rhodium(I) center in Rh(PCNHCP)(CO)Cl (5) is stabilized by the π-back bonding of CO ligand; a robust complex is, therefore, obtained. The solid-state structures of 2 and 3 were determined by X-ray diffraction. Complexes 3-5 are catalyst precursors for efficient, chemoselective hydrosilylation of alkynes. For the reaction between phenylacetylene and dimethylphenylsilane, a rapid hydrosilylation occurs, producing isomers of alkenylsilanes; then a slow isomerization pathway converts (Z)-alkenylsilane to its (E)-isomer. For 3, under catalytic condition, a facile reductive elimination of dichloromethane giving A is anticipated. The similarity in reactivity and selectivity between 3, 4 and 5 suggests the involvement of A as the active species in a common catalytic cycle.",
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Rhodium complexes of PCNHCP : Oxidative addition of dichloromethane and catalytic hydrosilylation of alkynes affording (E)-alkenylsilanes. / Zeng, Jing Yao; Hsieh, Meng Hua; Lee, Hon Man.

In: Journal of Organometallic Chemistry, Vol. 690, No. 24-25, 01.12.2005, p. 5662-5671.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Rhodium complexes of PCNHCP

T2 - Oxidative addition of dichloromethane and catalytic hydrosilylation of alkynes affording (E)-alkenylsilanes

AU - Zeng, Jing Yao

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AU - Lee, Hon Man

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N2 - New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP) 2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the presumably formed nucleophilic RhI(PCNHCP)Cl intermediate (A), undergoes a C-Cl bond activation of CH2Cl2 giving cis,mer-Rh III(PCNHCP)(CH2Cl)Cl2 (3) as the final product. Attempts to isolate A affords the oxidative degradation product of mer-RhIII(PCNHCP)Cl3 complex (4). In contrast, the rhodium(I) center in Rh(PCNHCP)(CO)Cl (5) is stabilized by the π-back bonding of CO ligand; a robust complex is, therefore, obtained. The solid-state structures of 2 and 3 were determined by X-ray diffraction. Complexes 3-5 are catalyst precursors for efficient, chemoselective hydrosilylation of alkynes. For the reaction between phenylacetylene and dimethylphenylsilane, a rapid hydrosilylation occurs, producing isomers of alkenylsilanes; then a slow isomerization pathway converts (Z)-alkenylsilane to its (E)-isomer. For 3, under catalytic condition, a facile reductive elimination of dichloromethane giving A is anticipated. The similarity in reactivity and selectivity between 3, 4 and 5 suggests the involvement of A as the active species in a common catalytic cycle.

AB - New rhodium complexes of PCNHCP have been synthesized by using the silver transfer reagent, [Ag3(PCNHCP) 2Cl]Cl2 (2). In the reaction between 2 and [Rh(COD)Cl]2 in dichloromethane, the presumably formed nucleophilic RhI(PCNHCP)Cl intermediate (A), undergoes a C-Cl bond activation of CH2Cl2 giving cis,mer-Rh III(PCNHCP)(CH2Cl)Cl2 (3) as the final product. Attempts to isolate A affords the oxidative degradation product of mer-RhIII(PCNHCP)Cl3 complex (4). In contrast, the rhodium(I) center in Rh(PCNHCP)(CO)Cl (5) is stabilized by the π-back bonding of CO ligand; a robust complex is, therefore, obtained. The solid-state structures of 2 and 3 were determined by X-ray diffraction. Complexes 3-5 are catalyst precursors for efficient, chemoselective hydrosilylation of alkynes. For the reaction between phenylacetylene and dimethylphenylsilane, a rapid hydrosilylation occurs, producing isomers of alkenylsilanes; then a slow isomerization pathway converts (Z)-alkenylsilane to its (E)-isomer. For 3, under catalytic condition, a facile reductive elimination of dichloromethane giving A is anticipated. The similarity in reactivity and selectivity between 3, 4 and 5 suggests the involvement of A as the active species in a common catalytic cycle.

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