The carbonylation of methylacetate to acetic anhydride catalysed by [CpRh(CO)2] in the absence of hydrogen

Marr, Andrew C.; Lightfoot, Philip; Ditzel, Evert J.; Poole, Andrew D.; Schwarz, Gary P.; Foster, Douglas F.; Cole‐Hamilton, David J.

doi:10.1016/s1387-7003(00)00157-x

Cited by 7 publications

(19 citation statements)

References 8 publications

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“…The two-dimensional spectra were recorded on a Bruker Avance 300. Broad band decoupling was used for 13 C spectra and 31 P spectra. 1 H and 13 C NMR spectra were referenced internally to deuteriated solvents and are reported relative to TMS.…”

Section: Methodsmentioning

confidence: 99%

“…Broad band decoupling was used for 13 C spectra and 31 P spectra. 1 H and 13 C NMR spectra were referenced internally to deuteriated solvents and are reported relative to TMS. 31 P chemical shifts are to high frequency of external H 3 PO 4 (85%).…”

Section: Methodsmentioning

confidence: 99%

“…[Cp*Rh(CO) 2 ] proved to be highly active for the carbonylation of methyl ethanoate to ethanoic anhydride, 13 but the most promising results were obtained using [Cp*Co(CO) 2 ] in the presence of PEt 3 . 14 At 100 bar and 120 • C, this system gave an initial rate of methanol carbonylation of 44 mol dm −3 h −1 , 1.5 times the rate using the same concentration of [RhI 2 (CO) 2 ] − under the same conditions and faster than obtained in the commercial rhodium based systems at 180 • C (ca.…”

Section: Introductionmentioning

confidence: 99%

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The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

et al. 2006

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2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C(5)R'(4)(CH(2))(2)PR(2)] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C(5)R'(4)(C(2)H(4)) with LiPR(2). C(5)Et(4)HSiMe(2)CH(2)PMe(2), was prepared from reaction of Li[C(5)Et(4)] with Me(2)SiCl(2) followed by Me(2)PCH(2)Li. The lithium salts were reacted with [RhCl(CO)(2)](2), [IrCl(CO)(3)] or [Co(2)(CO)(8)] to give [M(C(5)R'(4)(CH(2))(2)PR(2))(CO)] (M = Rh, R = Et, R' = H or Me, R = Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (Cp' = C(5)Me(4)), the most electron rich of the complexes. [Rh(C(5)Et(4)SiMe(2)CH(2)PMe(2))(CO)] may be a dimer. [Co(2)(CO)(8)] reacts with C(5)H(5)(CH(2))(2)PEt(2) or C(5)Et(4)HSiMe(2)CH(2)PMe(2) (L) to give binuclear complexes of the form [Co(2)(CO)(6)L(2)] with almost linear PCoCoP skeletons. [Rh(Cp'(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH(2))(2)PPh(2))(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI(2)(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt(3))(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH(2))(2)PEt(2))I(2)], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH(2))(2)PEt(2))(CO)]. Neither of [M(Cp'(CH(2))(2)PEt(2))(CO)] (M = Co or Ir) was active for methanol carbonylation under these conditions, nor under many other conditions investigated, except that [Ir(Cp'(CH(2))(2)PEt(2))(CO)] showed some activity at higher temperature (190 degrees C), probably as a result of degradation to [IrI(2)(CO)(2)](-). [M(Cp'(CH(2))(2)PEt(2))(CO)] react with MeI to give [M(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] (M = Co or Rh) or [Ir(Cp'(CH(2))(2)PEt(2))Me(CO)]I. The rates of oxidative addition of MeI to [Rh(C(5)H(4)(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are 62 and 1770 times faster than to [Cp*Rh(CO)(2)]. Methyl migration is slower, however. High pressure NMR studies show that [Co(Cp'(CH(2))(2)PEt(2))(CO)] and [Cp*Rh(PEt(3))(CO)] are unstable towards phosphine oxidation and/or quaternisation under methanol carbonylation conditions, but that [Rh(Cp'(CH(2))(2)PEt(2))(CO)] does not exhibit phosphine degradation, eventually producing inactive [Rh(Cp'(CH(2))(2)PEt(2))I(2)] at least under conditions of poor gas mixing. The observation of [Rh(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] under methanol carbonylation conditions suggests that the rhodium centre has become so electron ...

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

et al. 2006

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“…To this end, during the last decade several groups have investigated the use of group 9 metal complexes containing a range of ligands as catalysts for methanol carbonylation. [23] Examples are the application of monodentate [24,25] and bidentate phosphane ligands [26][27][28][29][30][31][32][33] as well as cyclopentadienyl ligands [34,35] and combinations thereof. [36] Nitrogen-based ligands such as diimines and pyridine ligands have also been investigated.…”

Section: Introductionmentioning

confidence: 99%

Dicarbonylrhodium(I) Complexes of Bipyridine Ligands with Proximate H‐Bonding Substituents and Their Application in Methyl Acetate Carbonylation

Conifer

Law²,

Sunley³

et al. 2011

Eur J Inorg Chem

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A series of cationic cis-dicarbonylrhodium(I) complexes [Rh(L)(CO) 2 ]SbF 6 has been prepared containing 2,2Ј-bipyridine ligands with proximate H-bonding substituents R in the 6-and 6Ј-position (R = OH, NH 2 , COOEt and PO(OEt) 2 ). The solid-state structures have been determined by X-ray crystallography for the complexes where R = OH, NH 2 and COOEt. The molecular structures have revealed metal-metal and π-π interactions between the square-planar complexes resulting in the formation of molecular chains in the solid state.

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“…Various studies have been carried out on the use of tertiary phosphines and we have shown that the use of triethyl phosphine rhodium complexes as catalysts for this reaction leads to higher activity than that obtained with the unmodified rhodium complex under industrial conditions, but the catalyst is unstable to phosphine loss. 7, 8 High rates for methyl acetate carbonylation to acetic anhydride were obtained when using [Cp*Rh(CO) 2 ] (Cp* = C 5 Me 5 , which is also highly electron donating), 9 but catalysts obtained using [Cp*M(CO) 2 ]/PEt 3 (M = Co or Rh) were unstable, although the Co system showed very a EaStCHEM, School of Chemistry, University of St. Andrews, St. Andrews, Fife, Scotland KY16 9ST. E-mail: djc@st-and.ac.uk; Fax: +44 (0)1334-463808; Tel: +44 (0) high initial rates.…”

Section: Introductionmentioning

confidence: 99%

Rhodium catalysed methanol carbonylation in the presence of bis(ditertiarybutylphosphinomethyl)benzene

et al. 2007

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Catalysts prepared in situ from 1,2-(Bu t 2 PCH 2 ) 2 C 6 H 4 (DTBPMB) and [RhCl(CO) 2 ] 2 catalyse the carbonylation of methanol in the presence of MeI at rates (4.12 and 8.90 × 10 −4 mol dm −3 s −1 at 150 and 180 • C respectively) faster than those in the absence of added phosphine, although they decompose to [RhI 2 (CO) 2 ] − over time. HPIR studies suggest that MeI adds to [Rh(DTBPMB)X(CO)] (X = Cl or I), which have been isolated and fully characterised, to give [Rh(DTBPMB)MeI 2 (CO)]. [Rh(DTBPMB)MeI 2 (CO)] reacts with CO to give [Rh(DTBPMB)(C(O)Me)I 2 (CO)], but that methanol promotes decomposition to [RhI 2 (CO) 2 ] − and [1,2-(MeBu t 2 PCH 2 ) 2 C 6 H 4 )][I 3 ] 2 , which has been isolated and characterised. HPNMR studies show that [Rh(DTBPMB)Cl(CO)] reacts with CO to give [Rh(DTBPMB)Cl(CO) 2 ], which is square pyramidal with an apical Cl.

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The carbonylation of methylacetate to acetic anhydride catalysed by [CpRh(CO)2] in the absence of hydrogen

Cited by 7 publications

References 8 publications

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium

Dicarbonylrhodium(I) Complexes of Bipyridine Ligands with Proximate H‐Bonding Substituents and Their Application in Methyl Acetate Carbonylation

Rhodium catalysed methanol carbonylation in the presence of bis(ditertiarybutylphosphinomethyl)benzene

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