Structural Aspects of Copper-Mediated Atom Transfer Radical Polymerization with a Novel Tetradentate Bisguanidine Ligand
This contribution reports the synthesis of the novel tetradentate bisguanidine ligand 2′,2′‐[ethane‐1, 2‐diylbis(methylazanediyl)]bis(ethane‐2, 1‐diyl)bis(1, 1, 3, 3‐tetramethylguanidine) (L1, TMG2dmtrien), which combines two weak amine and two strong guanidine donor functions. Two new copper(II) co...
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Published in | Zeitschrift für anorganische und allgemeine Chemie (1950) Vol. 638; no. 11; pp. 1683 - 1690 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English German |
Published |
Weinheim
WILEY-VCH Verlag
01.09.2012
WILEY‐VCH Verlag |
Subjects | |
Online Access | Get full text |
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Summary: | This contribution reports the synthesis of the novel tetradentate bisguanidine ligand 2′,2′‐[ethane‐1, 2‐diylbis(methylazanediyl)]bis(ethane‐2, 1‐diyl)bis(1, 1, 3, 3‐tetramethylguanidine) (L1, TMG2dmtrien), which combines two weak amine and two strong guanidine donor functions. Two new copper(II) complexes were isolated and structurally characterized as complexes [Cu(TMG2dmtrien)][Br]2·3MeCN (C1[Br]2·3MeCN) and [Cu(TMG2dmtrien)][Cl]2·3MeCN (C2[Cl]2·3MeCN). The cations C1 and C2 [Cu(TMG2dmtrien)]2+ show a square‐planar coordination environment and are chiral with both enantiomers being observed in the unit cell. We investigated the application of L1 in copper‐mediated styrene ATRP. L1 shows with CuBr and PEBr as initiator a high polymerization activity according to the polymerization rate. First order kinetics confirm the living character of the polymerization. However, the deviation of molecular weights from theoretical molecular weights and the broad molecular weight distributions hint for a low controlled ATRP. The ATRP with further copper(I) salts {CuCl, [Cu(MeCN)4]BF4 and [Cu(MeCN)4]PF6} and PECl and PEBr as initiators were investigated as well. Herein the use of [Cu(MeCN)4]PF6 with PECl led to promising results. |
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Bibliography: | Dedicated to Professor Klaus Jurkschat on the Occasion of His 60th Birthday Bundesministerium für Bildung und Forschung istex:8E22E052F96BE98C5A5CEC894D1866C0E17B94FD Deutsche Forschungsgemeinschaft Supporting Information for this article is available on the WWW under http://dx.doi.org/10.1002/zaac.201200092 or from the author. Fonds der Chemischen Industrie ark:/67375/WNG-PD3X8G99-F ArticleID:ZAAC201200092 http://dx.doi.org/10.1002/zaac.201200092 or from the author. Supporting Information for this article is available on the WWW under |
ISSN: | 0044-2313 1521-3749 |
DOI: | 10.1002/zaac.201200092 |