Chemistry of metal hydrides. VIII. Hydrolysis of transition metal alkoxycarbonyls and a kinetic study of the hydrolysis of trans-[PtCl(CO)(R3P)2]BF4

Clark, H. C.; Jacobs, W. J.

doi:10.1021/ic50087a043

Cited by 38 publications

(9 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It seems likely that protonation of CAT-COO • followed by a second reduction causes CO 2 to be eliminated, forming a hydride complex for the catalyst series under investigation. Similar behavior has been documented in isoelectronic platinum complexes and can result in the evolution of H 2 when a proton donor is available . Conversely, the reduction of CAT-COO • to form a 2 e – carboxylate moiety prior to protonation appears to be the appropriate sequence of events to initiate CO evolution.…”

Section: Resultssupporting

confidence: 62%

See 1 more Smart Citation

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

et al. 2018

View full text Add to dashboard Cite

Stabilizing interactions between charged electrocatalytic intermediates and a series of cationic residues were explored through the synthesis and characterization of six palladium bis(N-heterocyclic carbene) (NHC) complexes bearing unique onium functionalities. The presence of a positively charged, pendant substituent was found to mediate electrode kinetics and facilitate CO2 coordination to the catalytic center in a systematic fashion. The introduction of cationic moieties into this system is shown to enhance catalytic selectivity for the conversion of CO2 to CO by as much as 5 times that of an alkyl-bearing analog. A combination of electrochemical experiments and computational analysis demonstrates that catalyst performance benefits most from a bulky onium unit tethered to the catalyst through a flexible linker. This behavior was interpreted as a preference for a wide, hydrophobic reaction pocket that allows for the unhindered formation of catalytic intermediates and mediated interaction with the solution.

show abstract

Section: Resultssupporting

confidence: 62%

“…Similar behavior has been documented in isoelectronic platinum complexes and can result in the evolution of H 2 when a proton donor is available. 27 Conversely, the reduction of CAT-COO • to form a 2 e − carboxylate moiety prior to protonation appears to be the appropriate sequence of events to initiate CO evolution.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

et al. 2018

View full text Add to dashboard Cite

show abstract

“…The mechanism illustrated in path A involves addition of OH - to the hydroxycarbonyl group 40 to give a C(OH) 2 O function that subsequently decomposes via loss of HCO 3 - . A second proposal is that the reaction proceeds via a deprotonation mechanism (path B). , Reports on the relative stability of anionic metal CO 2 complexes, compared to the hydroxycarbonyl analogue, , led to the conclusion that decarboxylation occurs via a third mechanism (path C) which involves β-elimination of M−H from the M−CO 2 H functionality. The latter proposal is the most accepted, especially after the work by Pettit and co-workers, where a concerted elimination of CO 2 was suggested for the reaction rather than loss of CO 2 via a metallocarboxylic anion.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study of Gas-Phase Reactions of Fe(CO)₅ with OH^- and Their Relevance for the Water Gas Shift Reaction

1999

View full text Add to dashboard Cite

Revision of the homogeneously Fe(CO)5-catalyzed water gas shift reaction in the gas phase has been performed by means of quantum chemical calculations using gradient-corrected density functional theory (B3LYP) and ab initio methods at the CCSD(T) level. The classically assumed reaction path has been scrutinized step by step, and enlarged with novel mechanistic proposals. Our calculations lend additional credit to some of the previously accepted steps in the catalytic cycle, such as the initial attack of OH- to Fe(CO)5 and also to the recently accepted decarboxylation of (CO)4FeCOOH- (via a concerted mechanism involving a four-centered transition state), as well as to the acidification of the metal hydride (CO)4FeH- with water to yield the dihydride (CO)4FeH2. The present investigation also examines in terms of energies and activation barriers the existence/participation of new intermediates (in particular, a metalloformate species, a water−hydride adduct, and a dihydrogen complex), not mentioned in prior studies. Finally, a transition-metal-containing SN2-type reaction is explored for the last stages of this chemical process as a mechanistic alternative to regenerate the starting catalyst.

show abstract

“…Similar distortions have been observed in the [Pt4(p2-CO)5(PPhMe2)4]3 and [Pt2C02(CO)5(p2-CO)3(PPh3)2]5 complexes which have been formulated as 'butterfly' clusters and where Pt-Pt separations of 3.543(9) and 2.987(4) A, respectively, are considered as non-bonding distances. The assumption that the Pt(1) and Pt(4) atoms are not directly bonded to each other leads to a 16-electron configuration for the Pt(1) and Pt(4) atoms, an 18-electron closed shell for Pt (2) and Pt(3) and to a 'butterfly', rather than tetrahedral, formalism for the tetraplatinum cluster in (4).…”

Section: Known Chemistry Of the Binuclear Platinum Hydride [Pth2-mentioning

confidence: 99%

Dimerisation of a diplatinum to a tetraplatinum complex during catalysis of the water gas shift reaction: the X-ray crystal structure of [Pt₄(µ₂-CO)₂(µ₂-Ph₂PCH₂PPh₂)₃{Ph₂PCH₂P(:O)Ph₂}]

Frew¹,

Hill²,

Manojlović-Muir³

et al. 1982

J. Chem. Soc., Chem. Commun.

View full text Add to dashboard Cite

Chemistry of metal hydrides. VIII. Hydrolysis of transition metal alkoxycarbonyls and a kinetic study of the hydrolysis of trans-[PtCl(CO)(R3P)2]BF4

Cited by 38 publications

References 0 publications

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Theoretical Study of Gas-Phase Reactions of Fe(CO)₅ with OH^- and Their Relevance for the Water Gas Shift Reaction

Dimerisation of a diplatinum to a tetraplatinum complex during catalysis of the water gas shift reaction: the X-ray crystal structure of [Pt₄(µ₂-CO)₂(µ₂-Ph₂PCH₂PPh₂)₃{Ph₂PCH₂P(:O)Ph₂}]

Contact Info

Product

Resources

About

Chemistry of metal hydrides. VIII. Hydrolysis of transition metal alkoxycarbonyls and a kinetic study of the hydrolysis of trans-[PtCl(CO)(R3P)2]BF4

Cited by 38 publications

References 0 publications

Improved Electrocatalytic CO2 Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Improved Electrocatalytic CO2 Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Theoretical Study of Gas-Phase Reactions of Fe(CO)5 with OH- and Their Relevance for the Water Gas Shift Reaction

Dimerisation of a diplatinum to a tetraplatinum complex during catalysis of the water gas shift reaction: the X-ray crystal structure of [Pt4(µ2-CO)2(µ2-Ph2PCH2PPh2)3{Ph2PCH2P(:O)Ph2}]

Contact Info

Product

Resources

About

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Improved Electrocatalytic CO₂ Reduction with Palladium bis(NHC) Pincer Complexes Bearing Cationic Side Chains

Theoretical Study of Gas-Phase Reactions of Fe(CO)₅ with OH^- and Their Relevance for the Water Gas Shift Reaction

Dimerisation of a diplatinum to a tetraplatinum complex during catalysis of the water gas shift reaction: the X-ray crystal structure of [Pt₄(µ₂-CO)₂(µ₂-Ph₂PCH₂PPh₂)₃{Ph₂PCH₂P(:O)Ph₂}]