2011
DOI: 10.1002/ejic.201001197
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Synthesis and Application of New Guanidine Copper Complexes in Atom Transfer Radical Polymerisation

Abstract: The synthesis and copper coordination of the ligandsTMGdipae (L1) and DMEGdipae (L2) is reported. The solid‐state structures of obtained copper complexes [Cu(TMGdipae)Cl] (C1), [Cu(TMGdipae)Br] (C2), [Cu(TMGdipae)I] (C3), [Cu(DMEGdipae)Cl] (C4), [Cu(DMEGdipae)Br] (C5) and [Cu(DMEGdipae)I] (C6) show a trigonal distorted [2+1] coordination of the copper atom and indicate interesting binding properties of aliphatic guanidine hybrid ligands. DFT analysis and calculation of the intramolecular charge transfer by NBO… Show more

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Cited by 34 publications
(27 citation statements)
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“…The donor interplay between the guanidine and quinoline units as well as the large steric encumbrance of the guanidine units were crucial for the entatic coordination. The guanidine units provide σ and π contributions to the metal bonding, and copper guanidine complexes have been studied intensively in coordination chemistry, bioinorganic chemistry and for polymerisation applications …”
Section: Introductionmentioning
confidence: 99%
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“…The donor interplay between the guanidine and quinoline units as well as the large steric encumbrance of the guanidine units were crucial for the entatic coordination. The guanidine units provide σ and π contributions to the metal bonding, and copper guanidine complexes have been studied intensively in coordination chemistry, bioinorganic chemistry and for polymerisation applications …”
Section: Introductionmentioning
confidence: 99%
“…Following our strategy of generating Cu complexes with intermediate coordination environments, we continued with guanidine–quinoline ligands and varied the guanidine moiety from tetramethylguanidine (TMG) to dimethylethyleneguanidine (DMEG), which is a slightly weaker donor. [14b] Herein, we report the resulting series of bis(chelate) Cu I and Cu II complexes in which the cationic units again have very similar structures. By XAS studies, we obtained insights into the solution structures and the impact of the anion.…”
Section: Introductionmentioning
confidence: 99%
“…The donor properties can be tuned through the choice of guanidine substituents, amine and spacers. These ligands have already been intensely investigated in bioinorganic coordination chemistry [12][13][14][15][16][17][18], but also in the ATRP of styrene [19][20][21][22][23][24]. In all of these studies, it appeared that the polyfunctional guanidines support the oxidation state change from Cu(I) over Cu(II) to Cu(III) and stabilize the corresponding complexes excellently.…”
Section: Introductionmentioning
confidence: 99%
“…52) [190]. The molecular structure of the complex as well as DFT calculations revealed a stronger donation of the TMG unit in TMGd i pae than the respective DMEG unit.…”
Section: Guanidines In Copper-mediated Atom Transfer Radical Polymerimentioning
confidence: 94%
“…For bidentate ligands, it should be noted that they are generally used in a 2:1 ratio towards copper for controlled Fig. 50 Left, the bidentate ethylene-bridged bis(imidazolin-2-imine) ligand (BLiPr) synthesised by Petrovic et al; right, the CuCl complex used in ATRP of styrene [43] [190] polymerisation reactions. However, in this particular case, polymerisations were also conducted successfully in a 1:1 ratio.…”
Section: Guanidines In Copper-mediated Atom Transfer Radical Polymerimentioning
confidence: 99%