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

Dirnberger, Thomas; Werner, Helmut

doi:10.1002/cber.19921250906

Cited by 14 publications

(2 citation statements)

References 24 publications

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“…In this context it should be mentioned that Esteruelas, Oro, et al reported the preparation of the four-coordinate iridium(I) complex [Ir(κ 2 -acac){η 2 -CH 2 CHC(O)Me}(PCy 3 )] from [Ir(κ 2 -acac)(C 8 H 14 )(PCy 3 )] and methyl vinyl ketone and its thermal rearrangement to a mixture of two six-coordinate hydrido(vinyl)iridium(III) stereoisomers . Regarding the supposed intermediate trans -[IrCl{η 2 -CH 2 CHC(O)Me}(P i Pr 3 ) 2 ], initially formed in the reaction of trans -[IrCl(C 8 H 14 )(P i Pr 3 ) 2 ] with methyl vinyl ketone, we note that we had previously isolated the rhodium counterpart trans -[RhCl{η 2 -CH 2 CHC(O)Me}(P i Pr 3 ) 2 ], which slowly rearranges at room temperature to give the C−H activation product [RhH(Cl){κ 2 ( C , O )-CHCHC(Me)O}(P i Pr 3 ) 2 ] in high yield …”

Section: Resultsmentioning

confidence: 99%

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

Dirnberger

Werner

2005

Organometallics

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The reaction of the in situ generated cyclooctene iridium(I) derivative trans- [IrCl(C 8 H 14 )-(PiPr 3 ) 2 ] with methyl vinyl ketone and other Michael systems RCHdC(R′)C(O)R′′ (R ) H, Me, Ph, OMe; R′ ) H, Me, iPr; R′′ ) H, Me, OMe, NH 2 , NMe 2 ) resulted in the formation of the octahedral hydrido(vinyl)iridium(III) complexes [IrH(Cl){κ 2 (C,O)-C(R)dC(R′)C(R′′)dO}-(PiPr 3 ) 2 ] (2-13) with the vinyl ligand coordinated in a bidentate fashion. Treatment of trans-[IrCl(C 8 H 14 )(PiPr 3 ) 2 ] with methyl acrylate and either dimethyl fumarate or dimethyl maleate afforded the iridium(I) compounds trans-[IrCl(η 2 -RCHdCHCO 2 Me)(PiPr 3 ) 2 ] (15, 16), which thermally or photochemically rearrange to the thermodynamically more stable iridium(III) isomers [IrH(Cl){κ 2 (C,O)-C(R)dCHC(OMe)dO}(PiPr 3 ) 2 ] (17, 18) by intramolecular C-H activation. The reaction of trans-[IrCl(C 8 H 14 )(PiPr 3 ) 2 ] with PhCHdCHC(O)Ph gave a 1:1 mixture of the isomeric iridium(III) complexes [IrH(Cl){κ 2 (C,O)-C(Ph)dCHC(Ph)dO}(PiPr 3 ) 2 ] (19) and [IrH(Cl){κ 2 (C,O)-C 6 H 4 C(CHdCHPh)dO}(PiPr 3 ) 2 ] (20), which were separated by column chromatography. From trans-[IrCl(C 8 H 14 )(PiPr 3 ) 2 ] and acrylic acid both [IrH(Cl)-{κ 2 (C,O)-CHdCHC(OH)dO}(PiPr 3 ) 2 ] (21) and [IrH(Cl){κ 2 (O,O)-O 2 CCHdCH 2 }(PiPr 3 ) 2 ] (22) were obtained. While the attempted hydrogenation of [IrH(Cl){κ 2 (C,O)-CHdCHC(Me)dO}-(PiPr 3 ) 2 ] (2) with Pd/C as the catalyst led to the formation of [IrH 2 (Cl)(PiPr 3 ) 2 ] (24) and ethyl methyl ketone, the same starting material reacted with a solution of Cl 2 in chloroform to give the dichloro vinyl complex [IrCl 2 {κ 2 (C,O)-CHdC(Cl)C(Me)dO}(PiPr 3 ) 2 ] (27) in virtually quantitative yield. The reaction of both 2 and [IrH(I){κ 2 (C,O)-CHdCHC(Me)dO}(PiPr 3 ) 2 ] (29) with CO afforded the carbonyl compounds [IrH(X){η 1 -(Z)-CHdCHC(O)Me}(CO)(PiPr 3 ) 2 ] (31, 32) by partial opening of the chelate bond. Similarly to the Ir(PiPr 3 ) 2 counterparts, a series of (olefin)iridium(I) and hydrido(vinyl)iridium(III) compounds with Ir(PMetBu 2 ) 2 as a molecular unit were also prepared. Most remarkably, treatment of trans-[IrCl(η 2 -CH 2 d CHC(O)H)(PMetBu 2 ) 2 ] (43) with in situ generated trans-[IrCl(C 8 H 14 )(PMetBu 2 ) 2 ] led to a clean cleavage of coordinated acrolein to CO and ethene and afforded a 1:1 mixture of trans-[IrCl(CO)(PMetBu 2 ) 2 ] (44) and trans-[IrCl(C 2 H 4 )(PMetBu 2 ) 2 ] (45), respectively.

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Section: Resultsmentioning

confidence: 99%

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

Dirnberger

Werner

2005

Organometallics

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“…After stirring for 20 min at room temperature, the solvent was removed and from the residue, after recrystallization from pentane ( -78 "C), an orange-yellow microcrystalline solid was obtained: yield 38 mg (78%), m.p. 11 6 31.93 [d,J(RhC) 13.9 Hz, C,H,], 25.30 (s, AsCHCH,), 22.60 and 21.54 (s,AsCHCH,).…”

Section: Trans-[rhc1(co)(priasch2ch20mementioning

confidence: 99%

A series of rhodium(I) complexes, including carbene, vinylidene and allenylidene derivatives, with the bifunctional arsine Pri 2AsCH2CH2OMe as ligand

Schwab¹,

Werner²

1994

J. Chem. Soc., Dalton Trans.

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Synthese und Struktur von [Rh₂(μ1‐NO)(μ1‐H)(PiPr₃)₄]: Ein chiraler, NO‐und Hydrid‐verbrückter Rhodium(0)1‐Zweikernkomplex

1993

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Key Words: Rhodium hydrido complexes 1 Binuclear rhodium complex, molecular structure of 1 NO and hydride as bridging ligands f Axial chirality Synthesis and Structure of [Rhz(p-N0)(pH)(PiPr&]: A Chiral. NOand Hydride-Bridged Binuclear Rhodium(0) Complex The reaction of RhC1, . 3 HzO, PiPr,, iPrONa / iPrOH and N-* Die Position des Hydrido-Liganden wurde mit dem Programm HYDEX berechnet und nicht verfeinert.

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

Cited by 14 publications

References 24 publications

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

A series of rhodium(I) complexes, including carbene, vinylidene and allenylidene derivatives, with the bifunctional arsine Pri 2AsCH2CH2OMe as ligand

Synthese und Struktur von [Rh₂(μ1‐NO)(μ1‐H)(PiPr₃)₄]: Ein chiraler, NO‐und Hydrid‐verbrückter Rhodium(0)1‐Zweikernkomplex

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

Cited by 14 publications

References 24 publications

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

A Series of Hydrido(vinyl)iridium(III) Complexes That Are Thermodynamically More Stable than Their Olefin Iridium(I) Isomers

A series of rhodium(I) complexes, including carbene, vinylidene and allenylidene derivatives, with the bifunctional arsine Pri 2AsCH2CH2OMe as ligand

Synthese und Struktur von [Rh2(μ1‐NO)(μ1‐H)(PiPr3)4]: Ein chiraler, NO‐und Hydrid‐verbrückter Rhodium(0)1‐Zweikernkomplex

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

Synthese und Struktur von [Rh₂(μ1‐NO)(μ1‐H)(PiPr₃)₄]: Ein chiraler, NO‐und Hydrid‐verbrückter Rhodium(0)1‐Zweikernkomplex