Journal
DALTON TRANSACTIONS
Volume 51, Issue 35, Pages 13272-13287Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2dt01954j
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- Deutsche Forschungsgemeinschaft [CRC985]
- NFDI4Chem
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Copper bromide complexes based on a series of substituted guanidine-quinolinyl and -pyridinyl ligands were investigated, and the relationships between their molecular structures, spectroscopic and electronic properties were described. The study revealed that substituent positions and ligand flexibility have a significant impact on the stability and activity of the copper(ii) complexes.
Copper bromide complexes based on a series of substituted guanidine-quinolinyl and -pyridinyl ligands are reported. The ligand systems were chosen based on the large variation with regard to their flexibility in the backbone, different guanidine moieties and influence by electron density donating groups. Relationships between the molecular structures and spectroscopic and electronic properties are described. Beside the expected increase in activity by substituting the 4-position (NMe(2)vs. H), we showed that a higher flexibility, such as TMG vs. DMEG moiety, leads to a better stabilsiation of the copper(ii) complex. Due to the correlation of the potentials and K-ATRP values, the catalyst based on the ligand TMGm4NMe(2)py is the most active copper complex for ATRP with a bidentate ligand system. The combination of the strong donating abilities of dimethylamine pyridinyl, the donor properties of the TMG substituent, and the improved flexibility due to the methylene bridging unit leads to high activity. With all NMe2-substituted systems standard ATRP experiments were conducted and with more active NMe2-substituted pyridinyl systems, ICAR ATRP experiments of styrene were conducted. Low dispersities and ideal molar masses have been achieved.
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