Activation of Molecular Oxygen by a Molybdenum(IV) Imido Compound

Zwettler, Niklas; Grover, Nidhi; Belaj, Ferdinand; Kirchner, Karl; Mösch‐Zanetti, Nadia C.

doi:10.1021/acs.inorgchem.7b01768

Cited by 18 publications

(30 citation statements)

References 41 publications

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“…The Mo=O bond length in 2 is substantially elongated in comparison to the parent complex 1 , 1.8221(9) versus 1.7198(18) Å . Previously reported molybdenum(VI) oxido borane adducts showed a similar bond elongation .…”

Section: Resultssupporting

confidence: 85%

“…Addition of one equivalent of the Lewis acid B(C 6 F 5 ) 3 to the yellow solution of the molybdenum(VI) oxido imido precursor [MoO(N t Bu) L 2 ] ( 1 ) in pentane led to an immediate color change to deep‐red and subsequent formation of the Lewis adduct [Mo{OB(C 6 F 5 ) 3 }(N t Bu) L 2 ] ( 2 ) as a reddish precipitate. Compound 2 was isolated as a brick‐red solid in very good yield after purification (Scheme ).…”

Section: Resultsmentioning

confidence: 85%

“… UV/Vis absorption spectra of 1 , 2 and 3 a – 3 c in CH 2 Cl 2 and photograph of solutions of 2 and 3 a (CH 2 Cl 2 ).…”

Section: Resultsmentioning

confidence: 99%

“…Improved synthesis of [MoO(N t Bu)L 2 ] (1) : For the synthesis of 1 , a solution of 1 equiv of [MoO(N t Bu)Cl 2 (dme)] (1.13 g, 3.28 mmol) in acetonitrile (20 mL) was added dropwise to a suspension of 2 equiv HL (2.03 g, 6.57 mmol) and 2.2 equiv NEt 3 (1.01 mL, 7.22 mmol) in acetonitrile (20 mL) with stirring. The addition was accompanied by an immediate color change from bright yellow to deep‐red and the reaction mixture was stirred overnight.…”

Section: Methodsmentioning

confidence: 99%

“…For several years we have used molybdenum as an earth abundant and non‐toxic transition metal and develop high oxidation state molybdenum compounds, primarily for oxygen activation, oxygen‐atom‐transfer and oxidation reactions . With this in mind, we are exploring new concepts for the activation of metal peroxido and metal oxido moieties, with the latter being important intermediates in catalytic aerobic oxidation reactions, to increase the reactivity of this notoriously inert groups …”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 85%

“… UV/Vis absorption spectra of 1 , 2 and 3 a – 3 c in CH 2 Cl 2 and photograph of solutions of 2 and 3 a (CH 2 Cl 2 ).…”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs

et al. 2020

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Three molybdenum(VI) dioxido complexes [MoO 2 (L) 2 ] bearing Schiff base ligands were reacted with B(C 6 F 5 ) 3 to afford the corresponding adducts [MoO{OB(C 6 F 5 ) 3 }(L) 2 ], which were fully characterized. They exhibit Frustrated Lewis‐Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C 6 F 5 ) 3 }(L) 2 ] complex with L=2,4‐dimethyl‐6‐((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom‐Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of gem ‐dichloride and gem ‐dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.

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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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Activation of Molecular Oxygen by a Molybdenum(IV) Imido Compound

Abstract: Activation of molecular dioxygen at a molybdenum(IV) imido compound led to the isolation and full characterization of a remarkably stable transition-metal imidoperoxido complex.

Cited by 18 publications

References 41 publications

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

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

Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs

Interaction of Metal Oxido Compounds with B(C₆F₅)₃

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Activation of Molecular Oxygen by a Molybdenum(IV) Imido Compound

Abstract: Activation of molecular dioxygen at a molybdenum(IV) imido compound led to the isolation and full characterization of a remarkably stable transition-metal imidoperoxido complex.

Cited by 18 publications

References 41 publications

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

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

Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs

Interaction of Metal Oxido Compounds with B(C6F5)3

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Interaction of Metal Oxido Compounds with B(C₆F₅)₃