NDLI: Mechanistic studies on C–C reductive coupling of five-coordinate Rh(iii) complexes

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Cu-catalyzed aerobic oxidative amidation of aryl alkyl ketones with azoles to afford tertiary amides via selective C–C bond cleavage

Ruthenium-catalyzed alkoxycarbonylation of alkenes using carbon monoxide

A challenging Heck reaction of maleimides

Pd-catalyzed Heck cyclization and in situ hydrocarboxylation or hydromethenylation via a hydrogen borrowing strategy

Mechanistic studies on C–C reductive coupling of five-coordinate Rh(iii) complexes

Palladium-catalyzed intramolecular rearrangement of vinylidenecyclopropanes through C–C bond activation

Palladium catalyzed amide-oxazoline directed C–H acetoxylation of arenes

Brønsted base-catalyzed α-oxygenation of carbonyl compounds utilizing the [1,2]-phospha-Brook rearrangement

Transition-metal free oxidative aliphatic C–H fluorination

Efficient catalytic enantioselective Nazarov cyclizations of divinyl ketoesters

AlCl₃-catalyzed O-alkylative Passerini reaction of isocyanides, cinnamaldehydes and various aliphatic alcohols for accessing α-alkoxy-β,γ-enamides

Pd(ii)-catalyzed intermolecular enantioselective hydroamination of styrenes

Catalysis by electrons and holes: formal potential scales and preparative organic electrochemistry

Catalytic asymmetric synthesis of polysubstituted spirocyclopropyl oxindoles: organocatalysis versus transition metal catalysis

Correction: Transition metal-catalyzed direct remote C–H functionalization of alkyl groups via C(sp³)–H bond activation

Correction: Palladium catalyzed amide-oxazoline directed C–H acetoxylation of arenes

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Mechanistic studies on C–C reductive coupling of five-coordinate Rh(iii) complexes

Content Provider	Royal Society of Chemistry (RSC)
Author	Chen, Shanshan Su, Yan Han, Keli Li, Xingwei
Copyright Year	2015
Abstract	A series of five-coordinate Rh(III) vinyl complexes [Rh(N^C)(PAr3)2CHCHR]PF6 have been isolated as an intermediate in the coupling of a Rh(III) hydride with terminal alkynes. These Rh(III) vinyl complexes underwent aryl–vinyl reductive coupling to afford the Rh(I) chelating complex [Rh(N^C–CHCHR)–(PAr3)2]PF6 in high yields. Kinetic studies on the C–C reductive elimination revealed that the reaction kinetics is first order for a Rh(III)(4-trifluoromethyl)styryl complex with activation parameters of ΔH≠ = 20.9 kcal mol−1 and ΔS≠ = −6.1 eu. The electronic effects of the styryl group and the phosphine ligands on the rate of C–C reductive elimination were studied, and the rate constant decreases for a more electron-poor styryl group but increases for a less donating phosphine. The inhibitive effect of the added phosphine indicates that the dissociation of phosphine to afford a four-coordinate intermediate is involved, which was further supported by DFT calculations. Although intermediacy of a 4-coordinate species has been suggested, the active intermediate that directly undergoes C–C coupling was pinpointed to a five-coordinate cis phosphine complex on the basis of DFT studies. Significant accelerating effects were observed for oxygen donor solvents (THF-d8 and acetone-d6), possibly via efficient stabilization of the four-coordinate intermediate. However coordination of CO forms an inert six-coordinate Rh(III) complex. Thus an overall detailed mechanism of alkyne insertion and subsequent aryl–vinyl reductive elimination from the Rh(III) center has been proposed based on the experimental and theoretical data.
Starting Page	783
Ending Page	791
Page Count	9
File Format	HTM / HTML PDF
ISSN	20524129
Volume Number	2
Issue Number	7
Journal	Organic Chemistry Frontiers
DOI	10.1039/c5qo00049a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Oxidative addition Phosphine Hydride Dissociative Nucleophile Alkyne
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry

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Mechanistic studies on C–C reductive coupling of five-coordinate Rh(III) complexes

Oxidative Addition Reactions of Organorhodium(I) Complexes Containing the Tridentate Ligand 2,6-Bis(diphenylphosphanylmethyl)pyridine [Rh(PNP)R] (R = CH3, C6H5) with Iodine and Methyl Iodide and Investigation of the Reductive Elimination

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Mechanistic studies on C–C reductive coupling of five-coordinate Rh(iii) complexes

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