A latent s‐chelated ruthenium benzylidene initiator for ring‐opening metathesis polymerization

Diesendruck, Charles E.; Vidavsky, Yuval; Ben‐Asuly, Amos; Lemcoff, N. Gabriel

doi:10.1002/pola.23476

Cited by 64 publications

(55 citation statements)

References 34 publications

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“…In fact, [Ru(NHC)( t ‐BuCN) 4 + X – ]‐type catalysts (NHC = 1,3‐dimesitylimidazol‐2‐ylidene (IMes), 1,3‐dimesitylimidazolin‐2‐ylidene (IMesH 2 ), X = CF 3 COO, CF 3 SO 3 ) are the sole example of precatalysts that are in the presence of monomers but absence of (UV) light thermally latent at least up to 65 °C, also for highly reactive dicyclopentadiene (DCPD) . Apart from these precatalysts, the Lemcoff group reported on a series of latent and also UV‐active pre‐catalysts, too …”

Section: Introductionmentioning

confidence: 99%

Tailored molybdenum imido alkylidene N‐heterocyclic carbene complexes as latent catalysts for the polymerization of dicyclopentadiene

Beerhues

Sen

Schowner

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Three novel molybdenum imido alkylidene N‐heterocyclic carbene (NHC) pre‐catalysts, that is, Mo(N‐t‐Bu)(1‐(2,6‐diisopropylphenyl)‐3‐isopropyl‐4‐phenyl‐1H‐1,2,3‐triazol‐5‐ylidene)(CHCMe2Ph)(OTf)2 (I1, OTf = CF3SO3), Mo(N‐t‐Bu)(1‐(2,6‐diisopropylphenyl)‐3‐isopropyl‐4‐phenyl‐1H‐1,2,3‐triazol‐5‐ylidene)(CHCMe2Ph)(OTf)(t‐BuO) (I2) and Mo(N‐2,6‐Me2‐C6H3)(1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ylidene)(CHCMe2Ph)(OTf)2 (I3) are presented. Compared to complexes based on imidazol‐2‐ylidenes or imidazolin‐2‐ylidenes, (1‐(2,6‐diisopropylphenyl)‐3‐isopropyl‐4‐phenyl‐1H‐1,2,3‐triazol‐5‐ylidene) used in precatalysts I1 and I2 exerts a comparably strong trans effect to the triflate groups trans to the NHC, while (1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ylidene) used in I3 has a weaker trans effect on the triflate. In combination with a suitable second anionic ligand at molybdenum, that is, OTf, t‐BuO, compounds I1–I3 require higher temperatures to become active and can thus be used as truly room temperature latent pre‐catalysts, even for a highly reactive monomer such as dicyclopentadiene (DCPD). When used as latent precatalysts, I1–I3 offer access to poly‐DCPD with different degrees of cross‐linking and glass‐transition temperatures (Tg). © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3028–3033

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Section: Introductionmentioning

confidence: 99%

Tailored molybdenum imido alkylidene N‐heterocyclic carbene complexes as latent catalysts for the polymerization of dicyclopentadiene

Beerhues

Sen

Schowner

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…The catalyst displayed excellent latent properties in RCM, and even allowed for switching between “on–off” states repeatedly, by simple change of reaction temperature. Applying 60 to ROMP of a norbornene derivative resulted in equally good latent behavior . Again thermoswitchable behavior was observed.…”

Section: Metathesis‐derived Polymersmentioning

confidence: 96%

Latent and Delayed Action Polymerization Systems

Naumann

Buchmeiser

2014

Macromol. Rapid Commun.

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Various approaches to latent polymerization processes are described. In order to highlight recent advances in this field, the discussion is subdivided into chapters dedicated to diverse classes of polymers, namely polyurethanes, polyamides, polyesters, polyacrylates, epoxy resins, and metathesis-derived polymers. The described latent initiating systems encompass metal-containing as well as purely organic compounds that are activated by external triggers such as light, heat, or mechanical force. Special emphasis is put on the different chemical venues that can be taken to achieve true latency, which include masked N-heterocyclic carbenes, latent metathesis catalysts, and photolatent radical initiators, among others. Scientific challenges and the advantageous application of latent polymerization processes are discussed.

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“…The base of the pyramid comprises two chlorides trans to each other and two neutral r-donor ligands trans to each other. However, cis-dichloro species have also been described [4][5][6][7][8][9][10][11][12][13][14]. In these square pyramidal complexes the carbene carbon corresponds again to the apex of the pyramid, but the base is composed of two chloride ligands in mutual cis configuration, similar to the two neutral ligands.…”

Section: Introductionmentioning

confidence: 93%

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

2012

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Upon comparative NMR spectroscopy studies, the isomerization of newly disclosed dichloro [j 2 (C,O)-2-(N-propylaminocarbonyl)benzylidene][1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium from trans-dichloro configuration (SPY-5-31) to its thermodynamically more favored cis-dichloro derivative (with SPY-5-34 stereochemistry) was found to proceed via dissociation of one chloride ligand to form an intermediate cationic species. Furthermore, the performance of the trans-and the cis-dichloro derivatives as catalysts in ringclosing metathesis and as initiators in ring-opening metathesis polymerization was studied.

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A latent s‐chelated ruthenium benzylidene initiator for ring‐opening metathesis polymerization

Cited by 64 publications

References 34 publications

Tailored molybdenum imido alkylidene N‐heterocyclic carbene complexes as latent catalysts for the polymerization of dicyclopentadiene

Tailored molybdenum imido alkylidene N‐heterocyclic carbene complexes as latent catalysts for the polymerization of dicyclopentadiene

Latent and Delayed Action Polymerization Systems

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

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