Publication Data for: Regio‐ and Stereospecific Cyclopolymerization of α,ω‐Diynes by Cationic Molybdenum Imido Alkylidene N‐Heterocyclic Carbene Complexes

DOI

All primary data files and processed data of the journal article from Buchmeiser group. Spectroscopic data of the different polymers is put into folders for each polymer, data of table 1 is given as excel sheet, and an overview of the different catalysts as .tif image is attatched.

Abstract:

Both solvent‐free and acetonitrile‐containing cationic molybdenum imido alkylidene N‐heterocyclic carbene (NHC) complexes of the general formula [Mo(NR′)(CHCMe2R)(NHC)(X)+ A−] (R′ = 2,6‐Cl2‐C6H3, tBu, 2‐CF3‐C6H4, 2‐tBu‐C6H4, 2,6‐iPr2‐C6H3, 2,6‐Me2‐C6H3; R = Me, Ph; NHC = 1,3‐dimesitylimidazol‐2‐ylidene (IMes), 1,3‐di‐iPr‐imidazol‐2‐ylidene (IPr), 1,3,5‐triphenyl‐1,3,4‐triazol‐2‐ylidene); X = CF3SO3, C6F5O, OCH(CF3)2, OC(CF3)3, pyrrolide, C6F5COO, 2,6‐(CF3)2‐C6H3COO; A− = B(ArF)4−, Al(OC(CF3)3)4−), have been investigated for their propensity to cyclopolymerize 4,4‐disubstituted 1,6‐heptadiynes. All metal complexes contain a stereogenic (chiral) metal center, which accounts for the high reactivity and high regioselectivity of insertion (>99%) that are observed for all metal complexes, leading to highly conjugated, α‐insertion‐derived polyenes that are based on a highly regular polymer backbone and that show absorption maxima close to 600 nm. With the chiral monomer 4‐(ethoxycarbonyl)‐4‐(1S,2R,5S)‐(‐)‐menthoxycarbonyl‐1,6‐heptadiyne, high syndiospecifity (>99% syndiotactic) is observed. A mechanism explaining the high regio‐ and stereoselectivity is presented. Thus, α‐addition of the monomers proceeds chain‐end‐controlled trans to the NHC and is preferred over β‐addition through intramolecular Mo‐O chelation. Insertion of the monomers entails double inversion at the stereogenic metal center in the course of one complete monomer insertion.

Identifier
DOI https://doi.org/10.18419/darus-1691
Related Identifier IsCitedBy https://doi.org/10.1002/marc.201900398
Metadata Access https://darus.uni-stuttgart.de/oai?verb=GetRecord&metadataPrefix=oai_datacite&identifier=doi:10.18419/darus-1691
Provenance
Creator Probst, Patrick; Elser, Iris ORCID logo; Schowner, Roman ORCID logo; Benedikter, Mathis ORCID logo; Buchmeiser, Michael ORCID logo
Publisher DaRUS
Contributor Buchmeiser, Michael
Publication Year 2021
Funding Reference DFG 358283783 - SFB 1333 ; DFG BU 2174/19-1
Rights CC BY 4.0; info:eu-repo/semantics/openAccess; http://creativecommons.org/licenses/by/4.0
OpenAccess true
Contact Buchmeiser, Michael (Universität Stuttgart)
Representation
Resource Type Dataset
Format image/tiff; application/zip; text/tab-separated-values; application/vnd.openxmlformats-officedocument.spreadsheetml.sheet
Size 86990; 1647980; 9370459; 1338045; 1305488; 835979; 1300069; 1334032; 1305982; 1319782; 1314564; 1317617; 1310496; 1302894; 459; 12259
Version 1.0
Discipline Chemistry; Natural Sciences