Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]<sup>+</sup>

Woolley, Matthew J.; Khairallah, George N.; Silva, Gabriel da; Donnelly, Paul S.; Yates, Brian F.; O’Hair, Richard A. J.

doi:10.1021/om400358q

Cited by 43 publications

(35 citation statements)

References 119 publications

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“…(5)], thus closing the catalytic cycle of conversion of acetic acid into methane and carbon dioxide [Eq. (6)] [22,23] . It is important to confirm whether similar cycles can operate for larger carboxylic acids.…”

Section: Resultsmentioning

confidence: 99%

“…Species [(phen)M(CH 3 )] + were shown previously to react with acetic acid via Eq. 5, and the mechanism for this reaction was computationally studied in detail for M=Ni, Pd, and Pt [22,23] …”

Section: Resultsmentioning

confidence: 99%

“…(5)], thereby closing a catalytic cycle for the protodecarboxylation of acetic acid [Eq. (6)] [22,23]

true [(normalL) M (normalO_{2} CR)]^{+} \to CO_{2} + [(normalL) M (normalR)]^{+}

true [(normalL) M (CH_{3})]^{+} + CH_{3} CO_{2} normalH \to [(normalL) M (normalO_{2} CCH_{3})]^{+} + CH_{4}

true CH_{3} CO_{2} normalH \to CO_{2} + CH_{4}

…”

Section: Introductionmentioning

confidence: 99%

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Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

et al. 2020

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Using fatty acids as renewable sources of biofuels requires deoxygenation. While a number of promising catalysts have been developed to achieve this, their operating mechanisms are poorly understood. Here, model molecular systems are studied in the gas phase using mass spectrometry experiments and DFT calculations. The coordinated metal complexes [(phen)M(O2CR)]+ (where phen=1,10‐phenanthroline; M=Ni or Pd; R=CnH2n+1, n≥2) are formed via electrospray ionization. Their collision‐induced dissociation (CID) initiates deoxygenation via loss of CO2 and [C,H2,O2]. The CID spectrum of the stearate complexes (R=C17H35) also shows a series of cations [(phen)M(R’)]+ (where R’ < C17) separated by 14 Da (CH2) corresponding to losses of C2H4‐C16H32 (cracking products). Sequential CID of [(phen)M(R’)]+ ultimately leads to [(phen)M(H)]+ and [(phen)M(CH3)]+, both of which react with volatile carboxylic acids, RCO2H, (acetic, propionic, and butyric) to reform the coordinated carboxylate complexes [(phen)M(O2CR)]+. In contrast, cracking products with longer carbon chains, [(phen)M(R)]+ (R>C2), were unreactive towards these carboxylic acids. DFT calculations are consistent with these results and reveal that the approach of the carboxylic acid to the “free” coordination site is blocked by agostic interactions for R > CH3.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

et al. 2020

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“…For example, Fig. 5 shows a series of related metal complexes that react to varying degrees with background water in an ion trap [25].…”

Section: Ligand Association Reactionsmentioning

confidence: 99%

Mechanistic insights from mass spectrometry: examination of the elementary steps of catalytic reactions in the gas phase

Vikse

McIndoe

2015

Pure and Applied Chemistry

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Real-time mass spectrometric monitoring of speciation in a catalytic reaction while it is occurring provides powerful insights into mechanistic aspects of the reaction, but cannot be expected to elucidate all details. However, mass spectrometers are not limited just to analysis: they can serve as reaction vessels in their own right, and given their powers of separation and activation in the gas phase, they are also capable of generating and isolating reactive intermediates. We can use these capabilities to help fill in our overall understanding of the catalytic cycle by examining the elementary steps that make it up. This article provides examples of how these simple reactions have been examined in the gas phase.

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“…11) and a competing cycle (steps 1b and 3) for the water catalyzed decomposition of allyl acetate (eq. 12)[83][84][85].Brought to you by | NDSU Library Periodicals Authenticated Download Date | 6/8/15 11:48 AM [CH 3 CO 2 Pd(phen)] + > [CH 3 CO 2 Pt(phen)] + > [CH 3 CO 2 Ni(phen)] + . DFT calculations reveal that decarboxylation involves two transition states.…”

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confidence: 99%

Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters

O’Hair

2015

Pure and Applied Chemistry

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Metal-catalyzed decarboxylative coupling reactions of esters offer new opportunities for formation of C-C bonds with CO 2 as the only coproduct. Here I provide an overview of: key solution phase literature; thermochemical considerations for decarboxylation of esters and thermolysis of esters in the absence of a metal catalyst. Results from my laboratory on the use of multistage ion trap mass spectrometry experiments and DFT calculations to probe the gas-phase metal catalyzed decarboxylative cross-coupling reactions of allyl acetate and related esters are then reviewed. These studies have explored the role of the metal carboxylate complex in the gas phase decarboxylative coupling of allyl acetate proceeding via a simple twostep catalytic cycle. In Step 1, an organometallic ion, [CH 3 ML] +/-(where M is a group 10 or 11 metal and L is an auxillary ligand), is allowed to undergo ion-molecule reactions with allyl acetate to generate 1-butene and the metal acetate ion, [CH 3 CO 2 ML] +/-. In Step 2, the metal acetate ion is subjected to collision-induced dissociation to reform the organometallic ion and thereby close the catalytic cycle. DFT calculations have been used to explore the mechanisms of these reactions. The organometallic ions [CH 3 CuCH 3 ] -, [CH 3 Cu 2 ] + , [CH 3 AgCu] + and [CH 3 M(phen)] + (where M = Ni, Pd and Pt) all undergo C-C bond coupling reactions with allyl acetate (Step 1), although the reaction efficiencies and product branching ratios are highly dependant on the nature of the metal complex. For example, [CH 3 Ag 2 ] + does not undergo C-C bond coupling. Using DFT calculations, a diverse range of mechanisms have been explored for these C-C bond-coupling reactions including: oxidative-addition, followed by reductive elimination; insertion reactions and S N 2-like reactions. Which of these mechanisms operate is dependant on the nature of the metal complex. A wide range of organometallic ions can be formed via decarboxylation (Step 2) although these reactions can be in competition with other fragmentation channels. DFT calculations have located different types of transition states for the formation of [CH 3 CuCH 3 ] -, [CH 3 Cu 2 ] + , [CH 3 AgCu] + and [CH 3 M(phen)] + (where M = Ni, Pd and Pt). Of the catalysts studied to date, [CH 3 Cu 2 ] + and [CH 3 Pd(phen)] + are best at promoting C-C bond formation (Step 1) as well as being regenerated (Step 2). Preliminary results on the reactions of [C 6 H 5 M(phen)] + (M = Ni and Pd) with C 6 H 5 CO 2 CH 2 CH = CH 2 and C 6 H 5 CO 2 CH 2 C 6 H 5 are described.

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Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]⁺

Cited by 43 publications

References 119 publications

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

Mechanistic insights from mass spectrometry: examination of the elementary steps of catalytic reactions in the gas phase

Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters

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Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]+

Cited by 43 publications

References 119 publications

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

Gas‐Phase Models for the Nickel‐ and Palladium‐Catalyzed Deoxygenation of Fatty Acids

Mechanistic insights from mass spectrometry: examination of the elementary steps of catalytic reactions in the gas phase

Gas-phase studies of metal catalyzed decarboxylative cross-coupling reactions of esters

Contact Info

Product

Resources

About

Role of the Metal, Ligand, and Alkyl/Aryl Group in the Hydrolysis Reactions of Group 10 Organometallic Cations [(L)M(R)]⁺