Dramatic Increase in the Rate of Olefin Insertion by Coordination of Lewis Acids to the Oxo Ligand in Oxorhenium(V) Hydrides

Lambic, Nikola S.; Brown, Caleb A.; Sommer, Roger D.; Ison, Elon A.

doi:10.1021/acs.organomet.7b00291

Cited by 19 publications

(9 citation statements)

References 57 publications

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“…[55] The related hydrido complex [ReO(H)(DAP)] was furthermore used in af undamentals tudy on olefin insertioni nto the ReÀH bond. [56] Coordination of the Lewis acids B(C 6 F 5 ) 3 or Al(C 6 F 5 ) 3 to the terminal oxido group has ap ronounced impact on the electronic situation at the metal center,thereby significantly in- Figure 4. Zirconium oxidob orane adducts [Cp* 2 Zr{OB(C 6 F 5 ) 3 ] [31] (2,left) and [Cp 2 Zr{OB(C 6 F 5 ) 3 }Me] À [49] (23,right).…”

Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

“…The related hydrido complex [ReO(H)(DAP)] was furthermore used in a fundamental study on olefin insertion into the Re−H bond . Coordination of the Lewis acids B(C 6 F 5 ) 3 or Al(C 6 F 5 ) 3 to the terminal oxido group has a pronounced impact on the electronic situation at the metal center, thereby significantly increasing the rate of olefin insertion (rate constant increased by a factor of 10 7 to 10 11 ).…”

Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

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Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Zwettler

Mösch‐Zanetti

2019

Chemistry A European J

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Lewis acid-base pair chemistry has been placed on an ew level with the discovery that adduct formationb etween an electron donor (Lewis base) and acceptor (Lewis acid) can be inhibited by the introductiono fs teric demand, thus preserving the reactivityo fb oth Lewis centers, resulting in highly unusual chemistry.S ome of these highly versatile frustrated Lewis pairs (FLP) are capable of splitting avariety of small molecules, such as dihydrogen, in ah eterolytic and even catalytic manner.T his is in sharp contrastt oc lassical reactions where the inert substrate must be activated by am etal-basedc atalyst. Very recently,r esearch has emerged combining the two concepts,n amely the formationo fF LPs in whichametal compound represents the Lewis base, allowing for novel chemistry by using the heterolytic splitting power of both together with the redox reactivity of the metal. Such reactivity is not restricted to the metal center itself being aL ewis acid or base, also ancillary ligandsc an be used as part of the Lewis pair,s till with the benefit of the redox-active metal centern earby. This Minireview is designed to highlight the novel reactions arising from the combination of metal oxido transition-metal or rare-earthmetal compounds with the Lewis acid B(C 6 F 5 ) 3 .I tc overs a wide area of chemistry including small molecule activation, hydrogenation and hydrosilylation catalysis, and olefin metathesis, substantiating the broad influence of the novel concept. Futureg oals of this young and excitinga rea are briefly discussed.

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Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

Section: Influence Of Lewis Acid Coordination On Electronic Situationmentioning

confidence: 99%

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Zwettler

Mösch‐Zanetti

2019

Chemistry A European J

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“…The feasibility of the concept has very recently been demonstrated in dinitrogen complexes in which a Lewis acid led to the activation of the inert N 2 molecule . Further examples of reactivity enhancement upon coordination of B(C 6 F 5 ) 3 at metal oxido moieties have been reported by the groups of Schrock and Ison …”

Section: Introductionmentioning

confidence: 97%

Heterolytic Si−H Bond Cleavage at a Molybdenum‐Oxido‐Based Lewis Pair

Zwettler

Walg

Belaj

et al. 2018

Chemistry A European J

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The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C6F5)3 gave access to the Lewis adduct [Mo{OB(C6F5)3}(NtBu)L2] featuring reversible B−O bonding in solution. The resulting frustrated Lewis pair (FLP)‐like reactivity is reflected by the compound's ability to heterolytically cleave Si−H bonds, leading to a clean formation of the novel cationic MoVI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR3)(NtBu)L2][HB(C6F5)3]. These compounds possess properties highly unusual for molybdenum d0 species such as an intensive, charge‐transfer‐based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single‐crystal X‐ray diffraction analyses of 2 and 4 b, a derivative of 3 b featuring the [FB(C6F5)3]− anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B−H bond of the borohydride anion.

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“…These cooperative interactions are proposed to bias substrate coordination, stabilize high-energy transition states, and facilitate charge transfer . By emulating these properties in synthetic systems, transition-metal/Lewis acid (LA) systems have achieved improvements in reactivity and selectivity for organic reactions, , lowered overpotentials for electrocatalysis, , enabled small molecule activation, , and accelerated cross-coupling reactions . Because the mode of activation is substrate-dependent among these systems, the observed improvements to reactivity necessarily proceed through distinct mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Lewis Acid Effects on Calculated Ligand Electronic Parameters

Shanahan

Szymczak

2020

Organometallics

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Adding Lewis acids to coordinated ligands can impart systematic changes to their properties. We computationally explored the effects of acid-induced changes to the donor strength (Tolman electronic parameter) of 17 ligands, in addition to changes to the charge distribution and binding energies for a representative set of ligands. These results were compared using a combined experimental/computational study with cyanide. The combined results demonstrate: (1) large effects for the initial binding of even weak Lewis acids, with smaller changes as Lewis acidity is increased, (2) Lewis acid modifications afford smaller tunability than covalent substitution (Hammett parameters), and (3) binding energy provides a reasonable guide that can be used for designing cooperative interactions.

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Dramatic Increase in the Rate of Olefin Insertion by Coordination of Lewis Acids to the Oxo Ligand in Oxorhenium(V) Hydrides

Cited by 19 publications

References 57 publications

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Heterolytic Si−H Bond Cleavage at a Molybdenum‐Oxido‐Based Lewis Pair

Lewis Acid Effects on Calculated Ligand Electronic Parameters

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Dramatic Increase in the Rate of Olefin Insertion by Coordination of Lewis Acids to the Oxo Ligand in Oxorhenium(V) Hydrides

Cited by 19 publications

References 57 publications

Interaction of Metal Oxido Compounds with B(C6F5)3

Interaction of Metal Oxido Compounds with B(C6F5)3

Heterolytic Si−H Bond Cleavage at a Molybdenum‐Oxido‐Based Lewis Pair

Lewis Acid Effects on Calculated Ligand Electronic Parameters

Contact Info

Product

Resources

About

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

Interaction of Metal Oxido Compounds with B(C₆F₅)₃