2012
DOI: 10.1021/om300530p
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Five-Coordinate Rearrangements of Metallacyclobutane Intermediates during Ring-Opening Metathesis Polymerization of 2,3-Dicarboalkoxynorbornenes by Molybdenum and Tungsten Monoalkoxide Pyrrolide Initiators

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Cited by 58 publications
(76 citation statements)
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“…As reported previously, 37 (+)-DCMNBE and rac -DCMNBE are polymerized at approximately the same rate using W(O)(CHCMe 3 )(OHMT)(Pyr)(PMe 2 Ph). In contrast, (−)-DCBNBE and rac -DCBNBE are polymerized at different rates.…”
Section: Results and Discussionsupporting
confidence: 65%
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“…As reported previously, 37 (+)-DCMNBE and rac -DCMNBE are polymerized at approximately the same rate using W(O)(CHCMe 3 )(OHMT)(Pyr)(PMe 2 Ph). In contrast, (−)-DCBNBE and rac -DCBNBE are polymerized at different rates.…”
Section: Results and Discussionsupporting
confidence: 65%
“… 37 This mechanistic proposal is based on the fact that polymerization of (+)-DCMNBE (DCMNBE = 2,3-dicarbomethoxynorbornene) by 1a yields a polymer that contains ∼75% trans , isotactic dyads and 25% cis , syndiotactic dyads, while 1c yields a polymer that contains ∼92% trans , isotactic dyads and ∼8% cis , syndiotactic dyads ( Figure 1 ). 37 The olefinic protons in trans , isotactic polymer are inequivalent and on the same C=C bond (and therefore coupled to each other with J HH ∼ 16 Hz 37 ) while the olefinic protons in cis , syndiotactic polymer are inequivalent and on different C=C bonds (and therefore not coupled to each other). It was also shown that W(O)(CH- t -Bu)(OHMT)(Pyr)(PMe 2 Ph) polymerizes (+)-DCMNBE to give only cis , syndiotactic -poly[(+)-DCMNBE].…”
Section: Introductionmentioning
confidence: 99%
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“…While complexes 3a, 3b, 4, 5, 8, and 9 contain two triflate groups, compound 6 contains two different anionic ligands, i.e., one triflate and one hexafluro-2-propoxide group. As found for MAP-type catalysts [14,[25][26][27][28][29][30][31][32][33][34][35][36][37][38][39], no ligand scrambling is observed. Cationic 7 is unique: it represents the first cationic Mo imido alkylidene catalyst that displays substantial olefin metathesis reactivity (vide infra).…”
Section: Introductionmentioning
confidence: 68%
“…The following compounds were prepared using literature methods and full reaction details can be found in the supplementary information; Dimethyl bicyclo[2.2.1]hept-5-ene-3- endo -2- exo -dicarboxylate ( 17 ), 39, 51 6 16, 41 and 14 . 47 …”
Section: Methodsmentioning
confidence: 99%