Synthesis and structures of bimetallic silicon-containing imido alkylidene complexes of tungsten (R′O)2(ArN)WCH–SiR2–CHW(NAr)(OR′)2 (R=Me, Ph) and (R′O)2(ArN)WCH–SiMe2SiMe2–CHW(NAr)(OR′)2

Bochkarev, Andrey L.; Basova, G. V.; Grigorieva, Irina K.; Stolyarova, N. E.; Malysheva, I. P.; Fukin, Georgy K.; Баранов, Е. В.; Kurskii, Yurii A.; Bochkarev, L. N.; Abakumov, G. A.

doi:10.1016/j.jorganchem.2009.12.002

Cited by 9 publications

(4 citation statements)

References 23 publications

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“…As observed in the reaction of CP, the ROMPs of CO by the fluorinated alkoxo analogues ( 6 , 7 ) did not take place at 25 °C. As described in the introductory, − reported examples in ROMP of CO using alkylidene complexes with early transitions metals (especially without aid of AlCl 3 etc.) have been limited so far, , we thus believe that this is one of the unique characteristics for using this catalyst.…”

Section: Resultsmentioning

confidence: 99%

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Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization

Hou

Nomura

2016

J. Am. Chem. Soc.

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Ring-opening metathesis polymerization (ROMP) of various cyclic olefins especially using three (arylimido)vanadium(V)-alkylidene catalysts, V(CHSiMe3)(N-2,6-Cl2C6H3) (OC6F5) (PMe3)2 (3), V(CHSiMe3) (NR)[OC(CF3)3](PMe3)2 [R = Ph (6), 2,6-Cl2C6H3 (7)] have been explored. Complex 3 exhibited the highest catalytic activity (ex. TOF = 603 000 h(-1), 168 s(-1)) for ROMP of norbornene (NBE) among a series of (imido)vanadium(V)-alkylidenes, and the cis-specific living ROMPs of NBE proceeded with remarkable activities (TOF = 125 000-157 000 h(-1) at 25 °C) by the fluorinated alkoxo analogues (6, 7). The activities by 6, 7 increased at high temperature (50 and 80 °C) and/or upon addition of PMe3 without decrease in the cis selectivity (98%). The ROMPs in the presence of 1-hexene by 3, 7 proceeded without significant decrease in the activities, and the Mn values could be controlled by degree of chain transfer (cross metathesis). These dichlorophenylimido analogues (3, 7) were effective for ROMPs of various norbornene derivatives; ROMP of cyclooctene took place by 3, and the activity increased at high temperature (50, 80 °C).

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Section: Resultsmentioning

confidence: 99%

“…Although many successful achievements have been reported by adopting the molybdenum and tungsten catalysts, in fact, reported examples in thermally robust cis specific ( Z selective) olefin metathesis catalysts, ROMP of certain monomers such as cyclooctene − etc. have been limited and challenging subjects.…”

Section: Introductionmentioning

confidence: 99%

Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization

Hou

Nomura

2016

J. Am. Chem. Soc.

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“…In particular, the arylimido complexes containing fluorinated phenoxy ligand, V(CHSiMe 3 )(N-2,6-R 2 C 6 H 3 )(OC 6 F 5 )(PMe 3 ) 2 [R = Me, Cl ( 1 )], exhibited the remarkable activities for the living ROMP of NBE affording ultrahigh molecular weight polymers with narrow molecular weight distributions (e.g., M n = 2.05 × 10 6 , M w / M n = 1.12 by 1 ) . Complex 1 also polymerized cyclopentene (CPE) and cis -cyclooctene (COE), ,, and the activity in the ROMP of COE increased at high temperature. , …”

Section: Introductionmentioning

confidence: 99%

“…Since reported examples in ROMP of COE (and CPE, so-called low strain monomers) using alkylidene complexes with early transition metals still have been limited ,,− and since the reason for exhibiting the high activity by 1 would probably due to an electronic effect (formation of more electron-deficient metal-alkylidene), , in this paper, we thus prepared a series of (arylimido)vanadium(V)-alkylidene complexes containing pentachlorophenoxy ligand, V(CHSiMe 3 )(N-2,6-R 2 C 6 H 3 )(OC 6 Cl 5 )(PMe 3 ) 2 [R = H ( 2 ), Cl ( 3 ), F ( 4 ), CH 3 ( 5 ), Scheme ] and explored their catalyst performances in the ROMP of (so-called low strain) cyclic olefins. In particular, we demonstrate that the dichlorophenylimido analogue ( 3 ) exhibited the highest activities for ROMP of CPE, cycloheptene (CHPE), and COE, and the ROMPs of CHPE and COE proceeded in a (quasi) living manner with remarkably high activities (even at 80 °C) .…”

Section: Introductionmentioning

confidence: 99%

(Arylimido)Vanadium(V)-Alkylidenes Containing Chlorinated Phenoxy Ligands: Thermally Robust, Highly Active Catalyst in Ring-Opening Metathesis Polymerization of Cyclic Olefins

Chaimongkolkunasin

Nomura

2018

Organometallics

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A series of (imido)vanadium(V)-alkylidene complexes containing pentachlorophenoxy ligand of type, V(CHSiMe 3 )-(N-2,6-R 2 C 6 H 3 )(OC 6 Cl 5 )(PMe 3 ) 2 [R = H, Cl, F, CH 3 ], have been prepared, and the structure of V(CHSiMe 3 )(N-2,6-Me 2 C 6 H 3 )-(OC 6 Cl 5 )(PMe 3 ) 2 was determined by X-ray crystallographic analysis. Ring-opening metathesis polymerization (ROMP) of cyclic olefins such as norbornene (NBE), cyclopentene (CPE), cycloheptene (CHPE), and cis-cyclooctene (COE) using these alkylidene catalysts have been explored, and V(CHSiMe 3 )(N-2,6-Cl 2 C 6 H 3 )(OC 6 Cl 5 )(PMe 3 ) 2 showed higher activities in the ROMP of CPE, CHPE, and COE than those of the reported V(CHSiMe 3 )(N-2,6-Cl 2 C 6 H 3 )(OC 6 F 5 )(PMe 3 ) 2 . The activity in the ROMP of COE increased at high temperature until 120 °C, and the ROMPs of CHPE and COE proceeded without chain-transfer or termination (nor catalyst decomposition); the (quasi) living nature thus maintained even at 80 °C. The activities in the ROMPs of CHPE and COE (at 25 °C) increased upon addition of 1.0 equiv of B(C 6 F 5 ) 3 , whereas the activity in the ROMP of NBE became negligible upon the addition. The order in the activity in the ROMP of cyclic olefins displayed as COE ≪ CHPE < CPE ≪ NBE, which is different from not only that in the ring strain energy but also that reported in the ROMPs using ruthenium−carbene catalysts.

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Pushing the Bounds of Olefin Metathesis with Vanadium

Farrell

2021

Zeitschrift anorg allge chemie

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Olefin metathesis has been a key player in organic and polymer synthesis for over 50 years. While countless catalysts have been reported over this time, new compounds that offer improved selectivity, efficiency, robustness, and/or cost-effectiveness are still highly desired. This minireview will detail efforts made in this regard through the development of catalysts based on abundant and inexpensive vanadium. Special attention will be given to reports within the past three years concerning ringopening metathesis polymerization of low ring-strain cyclic olefins and expansion to other olefin metathesis transformations, such as cross-metathesis.

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Synthesis and structures of bimetallic silicon-containing imido alkylidene complexes of tungsten (R′O)2(ArN)WCH–SiR2–CHW(NAr)(OR′)2 (R=Me, Ph) and (R′O)2(ArN)WCH–SiMe2SiMe2–CHW(NAr)(OR′)2

Cited by 9 publications

References 23 publications

Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization

Ring-Opening Metathesis Polymerization of Cyclic Olefins by (Arylimido)vanadium(V)-Alkylidenes: Highly Active, Thermally Robust Cis Specific Polymerization

(Arylimido)Vanadium(V)-Alkylidenes Containing Chlorinated Phenoxy Ligands: Thermally Robust, Highly Active Catalyst in Ring-Opening Metathesis Polymerization of Cyclic Olefins

Pushing the Bounds of Olefin Metathesis with Vanadium

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