Rhodium catalyzed dimerization of vinyl ketones. NMR study of the dynamic behaviour of intermediate η2- and η4-methyl vinyl ketone complexes of rhodium(I)

Kovalev, I. P.; Kolmogorov, Yu. N.; Strelenko, Yu. À.; Игнатенко, А. В.; Vinogradov, M. G.; Nikishin, G. I.

doi:10.1016/0022-328x(90)87282-i

Cited by 7 publications

(1 citation statement)

References 13 publications

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“…The data are almost identical with those of the perchlorate [Rh( s - cis -η 4 -C 4 H 6 ) 2 (PPh 3 )]ClO 4 , previously prepared by Schrock and Osborn from [Rh(η 4 - nor -C 7 H 8 )(PPh 3 ) 2 ]ClO 4 and butadiene . The reaction of 2 with PMe 3 in the ratio of 1:1 in dichloromethane afforded a mixture of products among which, apart from the starting material, the cations [Rh(η 4 -C 4 H 6 ) 2 (PMe 3 )] + and [Rh(η 4 -C 4 H 6 )(PMe 3 ) 3 ] + could be identified by spectroscopic means . The more bulky phosphine P t Bu 2 Ph, which according to Tolman has the same cone angle as PCy 3 , reacted with 2 to give the uncharged complex 9 , isolated as an orange, slightly air-sensitive solid in 94% yield.…”

Section: Resultssupporting

confidence: 74%

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Bosch

Werner

2010

Organometallics

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Rhodium bis(diolefin) complexes of the general composition [Rh(η 4 -diene) 2 (L)]X (diene = butadiene, isoprene, 2,3-dimethylbutadiene; L = PiPr 3 , PCy 3 , PtBu 2 Me, AsiPr 3 , SbiPr 3 , CO, CNtBu, CN-2,6-C 6 H 3 iPr 2 ; X = CF 3 SO 3 , B(Ar f ) 4 ) were prepared from the nonionic compounds(2-4) as precursors. The reaction of 1 with 1,3-cyclohexadiene led to the formation of [(η 6 -C 6 H 6 )Rh(η 4 -C 6 H 8 )]CF 3 SO 3 , whereas from 1 and 6,6 0 -dimethylfulvene the unsymmetrical sandwich compound [{η 5 -C 5 H 4 CH-(CH 3 ) 2 }Rh{η 5 -C 5 H 4 C(dCH 2 )CH 3 }]CF 3 SO 3 was obtained. From [Rh{κ 2 -O 2 S(O)CF 3 }(PiPr 3 ) 2 ] and 1,3-cyclohexadiene or 6,6 0 -dimethylfulvene the four-coordinated diene complexes [Rh(η 4 -diene)-(PiPr 3 ) 2 ]CF 3 SO 3 were prepared, the cyclohexadiene derivative of which slowly rearranged at room temperature to cis,cis,trans-[Rh{κ 2 -O 2 S(O)CF 3 }(H) 2 (PiPr 3 ) 2 ] and benzene. Similarly, [Rh(η 4 -C 6 H 8 ){κ 2 -iPr 2 P(CH 2 ) 3 PiPr 2 }]CF 3 SO 3 , obtained from [Rh(η 4 -C 4 H 6 ){κ 2 -iPr 2 P(CH 2 ) 3 PiPr 2 }]CF 3 SO 3 and 1,3-cyclohexadiene, rearranged at 50 °C to [(η 6 -C 6 H 6 )Rh{κ 2 -iPr 2 P(CH 2 ) 3 PiPr 2 }]CF 3 SO 3 . The bis(butadiene) complexes [Rh(η 4 -C 4 H 6 ) 2 (PR 3 )]CF 3 SO 3 (R = iPr, Cy) reacted in CH 2 Cl 2 at ambient temperature to afford the neutral C-C coupling products [Rh(η 3 :η 3 -C 8 H 12 ){κ 1 -OS(O) 2 CF 3 }(PR 3 )], which upon treatment with NaB(Ar f ) 4 gave the ionic compounds [Rh(η 3 :η 3 -C 8 H 12 )(PR 3 )]B(Ar f ) 4 . The two isomers [Rh(η 4 -C 4 H 6 ) 2 (PR 3 )]CF 3 SO 3 and [Rh(η 3 :η 3 -C 8 H 12 ){κ 1 -OS(O) 2 CF 3 }(PR 3 )] are likely intermediates in the (cyclo)oligo-and polymerization of butadiene catalyzed by 1/PR 3 . While the oligomeric fraction predominantly consists of C 12 and C 16 olefinic hydrocarbons, the main component among the C 16 tetramers is cis,cis,trans,trans-1,5,9,13-cyclohexadecatetraene. † Part of the Dietmar Seyferth Festschrift. Dedicated to Professor Dietmar Seyferth in recognition of his scientific achievements and his prominent role as chief editor of Organometallics.(1) (a) Wilke, G.

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Section: Resultssupporting

confidence: 74%

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Bosch

Werner

2010

Organometallics

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Studien zur C–H‐Aktivierung, VIII, Hydrido(vinyl)rhodium(III)‐Komplexe aus [RhCl(PiPr₃)₂] und Olefinen

Dirnberger

Werner

1992

Chem. Ber.

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ChemInform Abstract: Rhodium‐Catalyzed Dimerization of Vinyl Ketones. NMR Study of the Dynamic Behavior of Intermediate η2‐ and η4‐Methyl Vinyl Ketone Complexes of Rhodium(I).

et al. 1990

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Rhodium catalyzed dimerization of vinyl ketones. NMR study of the dynamic behaviour of intermediate η2- and η4-methyl vinyl ketone complexes of rhodium(I)

Cited by 7 publications

References 13 publications

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Studien zur C–H‐Aktivierung, VIII, Hydrido(vinyl)rhodium(III)‐Komplexe aus [RhCl(PiPr₃)₂] und Olefinen

ChemInform Abstract: Rhodium‐Catalyzed Dimerization of Vinyl Ketones. NMR Study of the Dynamic Behavior of Intermediate η2‐ and η4‐Methyl Vinyl Ketone Complexes of Rhodium(I).

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Rhodium catalyzed dimerization of vinyl ketones. NMR study of the dynamic behaviour of intermediate η2- and η4-methyl vinyl ketone complexes of rhodium(I)

Cited by 7 publications

References 13 publications

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene

Studien zur C–H‐Aktivierung, VIII, Hydrido(vinyl)rhodium(III)‐Komplexe aus [RhCl(PiPr3)2] und Olefinen

ChemInform Abstract: Rhodium‐Catalyzed Dimerization of Vinyl Ketones. NMR Study of the Dynamic Behavior of Intermediate η2‐ and η4‐Methyl Vinyl Ketone Complexes of Rhodium(I).

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Studien zur C–H‐Aktivierung, VIII, Hydrido(vinyl)rhodium(III)‐Komplexe aus [RhCl(PiPr₃)₂] und Olefinen