Synthesis of (adamantylimido)vanadium(V)-alkyl complexes containing aryloxo ligands and their use as the catalyst precursors for ring-opening metathesis polymerization of norbornene, and ring-opening polymerization of tetrahydrofuran

Suzuki, Ken; Matsumoto, Yuichi; Nomura, Kotohiro

doi:10.1016/j.jorganchem.2011.06.013

Cited by 15 publications

(20 citation statements)

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“…The 31 P NMR spectrum of 2a showed a broad resonance . As described below, the reaction with C 6 F 5 OH in C 6 D 6 afforded V(CHSiMe 3 )(NAd)(OC 6 F 5 )(PMe 3 ) 2 ( 2b ) and the dialkyl analogues ( 3b and the PMe 3 adduct), and pure isolation of 2b from the mixture was not successful.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Hatagami

Nomura

2014

Organometallics

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V(CHSiMe3)(NAd)(CH2SiMe3)(PMe3)2 (1, Ad = 1-adamantyl) has been isolated from V(NAd)(CH2SiMe3)3 in the presence of PMe3 (excess, 12 equiv) upon heating, and the reaction of 1 with 2,6-Me2C6H3OH in n-hexane afforded V(CHSiMe3)(NAd)(O-2,6-Me2C6H3)(PMe3)2 (2a); structures of 1 and 2a have been determined by X-ray crystallography. Reaction of 1 with C6F5OH in C6D6 afforded a mixture of V(CHSiMe3)(NAd)(OC6F5)(PMe3)2 (2b) and V(NAd)(CH2SiMe3)2(OC6F5) (3b) and the PMe3 adduct (3b-PMe 3 ), and the consumption rate of 1 decreased upon addition of PMe3 or use of C6F5OD in place of C6F5OH, clearly suggesting that the reaction proceeds via coordination of C6F5OH and subsequent reaction with the alkylidene or the alkyl moiety. The catalytic activity in the ring-opening metathesis polymerization (ROMP) of norbornene by 1 increased upon addition of phenol; 1-C6F5OH catalyst showed a remarkable activity (TOF 20 000 h–1), affording high molecular weight polymer with a unimodal molecular weight distribution. Reactions with 2a,b with phenol afforded the bis(phenoxy) complexes, and it has been suggested that these reactions proceed via coordination of phenol and subsequent reaction with the alkylidene accompanying phenoxy exchange on the vanadium.

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Section: Resultsmentioning

confidence: 99%

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Hatagami

Nomura

2014

Organometallics

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“…In these papers, many vanadium imido complexes are treated with PMe 3 , resulting in α-elimination of an alkyl ligand to form alkylidene-containing catalysts which are active for ROMP with norbornene (Scheme ). − Notable observations from these studies are as follows: (1) ROMP did not proceed without addition of PMe 3 , (2) activities of arylimido catalysts were generally higher than those of the adamantylimido analogues, (3) fluoride substituents on the aryl group increased activities vs nonfluorinated analogues, and (4) polydispersities of polymers produced by catalysts 105 – 108 were much higher than those generated from other catalysts, such as Ru and Mo …”

Section: Catalytic Applications Of Homogeneous Vanadium Systemsmentioning

confidence: 98%

Catalytic Applications of Vanadium: A Mechanistic Perspective

et al. 2018

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The chemistry of vanadium has seen remarkable activity in the past 50 years. In the present review, reactions catalyzed by homogeneous and supported vanadium complexes from 2008 to 2018 are summarized and discussed. Particular attention is given to mechanistic and kinetics studies of vanadium-catalyzed reactions including oxidations of alkanes, alkenes, arenes, alcohols, aldehydes, ketones, and sulfur species, as well as oxidative C–C and C–O bond cleavage, carbon–carbon bond formation, deoxydehydration, haloperoxidase, cyanation, hydrogenation, dehydrogenation, ring-opening metathesis polymerization, and oxo/imido heterometathesis. Additionally, insights into heterogeneous vanadium catalysis are provided when parallels can be drawn from the homogeneous literature.

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“…The further in‐situ generation of vanadium alkylidene complex with addition of PMe 3 or at high temperature could lead to the ROMP of cyclic olefins. [ 12 ] Higher activities of binuclear complex system were observed in ROMP, especially the cyclic polymer was obtained and demonstrated.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Synthesis of Cyclic Polyolefin: Ring‐Opening Metathesis Polymerization by Binuclear Vanadium Complexes^†

Hou¹,

Chen²,

Gao³

et al. 2021

Chin. J. Chem.

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Ring-opening metathesis polymerization (ROMP) of norbornene by binuclear vanadium alkylidene in-situ formed from dialkyl complexes was investigated. Higher activities were observed by the binuclear system than mononuclear analogues. Especially the cyclic polymers were obtained and demonstrated. It is proposed that cyclic binuclear vanadium alkylidene was afforded due to the intramolecular chain-transfer reaction. The size of polymer ring could be adjusted by the vanadium catalyst structure and polymerization temperature. Similar results were also observed in the ROMP of cyclopentene.

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Synthesis of (adamantylimido)vanadium(V)-alkyl complexes containing aryloxo ligands and their use as the catalyst precursors for ring-opening metathesis polymerization of norbornene, and ring-opening polymerization of tetrahydrofuran

Cited by 15 publications

References 44 publications

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Catalytic Applications of Vanadium: A Mechanistic Perspective

Synthesis of Cyclic Polyolefin: Ring‐Opening Metathesis Polymerization by Binuclear Vanadium Complexes^†

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Synthesis of (adamantylimido)vanadium(V)-alkyl complexes containing aryloxo ligands and their use as the catalyst precursors for ring-opening metathesis polymerization of norbornene, and ring-opening polymerization of tetrahydrofuran

Cited by 15 publications

References 44 publications

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe3: Reactions of the Alkylidene Complexes with Phenols

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe3: Reactions of the Alkylidene Complexes with Phenols

Catalytic Applications of Vanadium: A Mechanistic Perspective

Synthesis of Cyclic Polyolefin: Ring‐Opening Metathesis Polymerization by Binuclear Vanadium Complexes†

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Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Synthesis of (Adamantylmido)vanadium(V)-Alkyl, Alkylidene Complex Trapped with PMe₃: Reactions of the Alkylidene Complexes with Phenols

Synthesis of Cyclic Polyolefin: Ring‐Opening Metathesis Polymerization by Binuclear Vanadium Complexes^†