Der Dihydridoiridium(III)-Komplex [IrH2Cl(PiPr3)2] als Molekülbaustein für unsymmetrische Rhodium-Iridiumund Iridium-Iridium-Zweikernverbindungen

Werner, Helmut; Nürnberg, Oliver; Wolf, Justin

doi:10.1002/1521-3749(200104)627:4<693::aid-zaac693>3.0.co;2-h

Cited by 6 publications

(2 citation statements)

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“…Shorter M−CO bonds of 5 (1.859(5) Å) and 6 (1.844(6) Å) as compared to those of 3 (1.88(1) Å) and 4 (1.89(1) Å) are observed. The C(2)−C(3) bonds of the alkynyl complexes 5 and 6 (1.196(6) and 1.206(6) Å, respectively) are longer than the standard value of the C⋮C bond (1.181 Å). , These structural parameters are reflected by a vinylene resonance form of the alkynyl complex having a strong π back-donation. The 13 C{ 1 H} NMR showed M−C α ⋮C β carbon signals at reasonable positions ( 5 , δ 128.32 (C α ), 135.27 (C β ); 6 , δ 110.91 (C α ), 128.47 (C β )).…”

Section: Resultsmentioning

confidence: 97%

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

et al. 2004

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2,2-Bis(2-phenylethyl)-1-methylenecyclopropane reacts with RhH(CO)(PPh 3 ) 3 at room temperature and with IrH(CO)(PPh 3 ) 3 at 70 °C to form the 3-butenyl complexes of these metals, M{η 1 :η 2 -CH 2 C(CH 2 CH 2 Ph) 2 CHdCH 2 }(CO)(PPh 3 ) 2 (1, M ) Rh; 2, M ) Ir). Heating 1 at 55 °C liberates 1,1-bis(2-phenylethyl)-1,3-butadiene, while the thermal reaction of 2 at 110 °C forms a mixture of 3-methyl-3-vinyl-1,5-diphenyl-1-pentene (48% NMR yield) and 3-methyl-3-vinyl-1,5-diphenylpentane (15% NMR yield). The reactions of excess amounts of 2,2-bis(2-phenylethyl)-1-methylenecyclopropane with RhH(CO)(PPh 3 ) 3 at 55 °C and with IrH-(CO)(PPh 3 ) 3 at 115 °C afford the alkenyl complexes trans-Rh{ 4), respectively. The reaction mechanisms are discussed on the basis of the results of the reactions under different conditions. HCtCC(CH 2 CH 2 Ph) 2 CH 3 reacts with MH(CO)(PPh 3 ) 3 (M ) Rh, Ir) to afford the alkynyl complexes trans-M{CtCC(CH 2 CH 2 Ph) 2 CH 3 }(CO)(PPh 3 ) 2 (5, M ) Rh; 6, M ) Ir) via oxidative addition of the C(alkyne)-H bond to the metal center and subsequent elimination of H 2 .

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Section: Resultsmentioning

confidence: 97%

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

et al. 2004

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“…The chemistry of transition metal alkynyls has been the subject of much interest in recent years. , These compounds have been investigated for a number of technological applications, in particular as molecular wires, − polymeric systems, , catalysts for polymerization, , liquid crystals, − organometallic catananes, dendrimers, , molecular scaffolds, luminescent materials, − and as materials for nonlinear optics (NLO). − Some systems have received more attention than others, and in particular, those containing platinum or palladium, ,,,,,− rhodium, ,− ruthenium, − rhenium, ,,, and osmium have received the bulk of the attention.…”

Section: Introductionmentioning

confidence: 99%

Mechanism of Formation of [(PMe₃)₃Rh(−C⋮C−R)₂(H)] via C−H Oxidative Addition: Isomerization, Alkyne Exchange, and Hydride Replacement

et al. 2001

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The mechanism of formation of mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 H] from [(PMe 3 ) 4 Rh(Me)] and terminal alkyne has been studied. The initial step of the reaction is the elimination of methane and the formation of the trigonal bipyramidal complex [(PMe 3 ) 4 Rh(-CtC-R)], a reaction that is complete in time of mixing at -78 °C. This intermediate undergoes an oxidative addition reaction with a second equivalent of alkyne to give fac-[(PMe 3 ) 3 Rh(-Ct C-R) 2 H] as the kinetic product. This fac isomer is not stable above -20 °C and isomerizes to the thermodynamic product mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 H]. fac-[(PMe 3 ) 3 Rh(-CtC-R) 2 H] will exchange alkynyl groups with free alkyne, a reaction that has a lower energetic barrier than the isomerization to mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 H]. Density functional theory studies on all stages of the formation of mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 H] have been carried out and give ground state energies in line with those experimentally observed. Once formed, mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 H] is configurationally stable and not prone to scrambling, although it will react with chloroform, whereupon the hydride is replaced by chloride. The initial product of this reaction is mer,trans-[(PMe 3 ) 3 Rh(-CtC-R) 2 Cl], and this compound has been studied by single-crystal X-ray diffraction. In solution mer,trans-[(PMe 3 ) 3 -Rh(-CtC-R) 2 Cl] isomerizes slowly to mer,cis-[(PMe 3 ) 3 Rh(-CtC-R) 2 Cl]. Scheme 2 Scheme 3 Mechanism of Formation of [(PMe 3 ) 3 Rh(-CtC-R) 2 (H)]

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Asymmetric Halogeno-Bridged Complexes: New Reagents in Organometallic Synthesis and Catalysis

Severin

2002

Chem. Eur. J.

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Der Dihydridoiridium(III)-Komplex [IrH2Cl(PiPr3)2] als Molekülbaustein für unsymmetrische Rhodium-Iridiumund Iridium-Iridium-Zweikernverbindungen

Cited by 6 publications

References 10 publications

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

Mechanism of Formation of [(PMe₃)₃Rh(−C⋮C−R)₂(H)] via C−H Oxidative Addition: Isomerization, Alkyne Exchange, and Hydride Replacement

Asymmetric Halogeno-Bridged Complexes: New Reagents in Organometallic Synthesis and Catalysis

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Der Dihydridoiridium(III)-Komplex [IrH2Cl(PiPr3)2] als Molekülbaustein für unsymmetrische Rhodium-Iridiumund Iridium-Iridium-Zweikernverbindungen

Cited by 6 publications

References 10 publications

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η1:η2-CH2CR2CHCH2)(CO)(PPh3)2andtrans-M(CHCHCMeR2)(CO)(PPh3)2(M = Rh, Ir, R = CH2CH2Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η1:η2-CH2CR2CHCH2)(CO)(PPh3)2andtrans-M(CHCHCMeR2)(CO)(PPh3)2(M = Rh, Ir, R = CH2CH2Ph)

Mechanism of Formation of [(PMe3)3Rh(−C⋮C−R)2(H)] via C−H Oxidative Addition: Isomerization, Alkyne Exchange, and Hydride Replacement

Asymmetric Halogeno-Bridged Complexes: New Reagents in Organometallic Synthesis and Catalysis

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C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

C−C and C−H Bond Activation of Dialkylmethylenecyclopropane Promoted by Rhodium and Iridium Complexes. Preparation and Structures of M(η¹:η²-CH₂CR₂CHCH₂)(CO)(PPh₃)₂andtrans-M(CHCHCMeR₂)(CO)(PPh₃)₂(M = Rh, Ir, R = CH₂CH₂Ph)

Mechanism of Formation of [(PMe₃)₃Rh(−C⋮C−R)₂(H)] via C−H Oxidative Addition: Isomerization, Alkyne Exchange, and Hydride Replacement