Synthesis and characterization of Cu(I) and Cu(II) complexes containing ketiminate ligands

Hsu, Sung‐Chi; Li, Chen Yi; Chiu, Ya Wen; Chiu, Mei Chun; Lien, Yu-Ling; Kuo, Pei Cheng; Lee, Hon Man; Huang, Jui Hsien; Cheng, Chih-Ming

doi:10.1016/j.jorganchem.2007.08.028

Cited by 16 publications

(14 citation statements)

References 44 publications

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“…Since Cu has higher affinity to N ligands, modification of acetylacetone by introduction of a diamine was envisaged to yield amine-functionalized β-ketimines, a well-known class of ligands that has already been used to generate Cu I derivatives. [12][13][14][15] We report here the synthesis and structural characterization of new copper(II) complexes incorporating these ligands, as well as a preliminary exploration of their ability to control the radical polymerization of styrene under reverse ATRP conditions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

2011

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The reaction of CuCl2 with R2NCH2CH2NHC(Me)=CHCO(Me) [R = Me (HL1) or Et (HL2)] in the presence of Et3N leads to the formation of complexes [CuCl(Ln)] [n = 1 (1), 2 (2)]. Whereas the solid‐state structure of compound 2 is mononuclear with a close to square‐planar arrangement of the ClON2 donor set, compound 1 adopts a dinuclear di‐μ‐chlorido arrangement in which two mononuclear units having essentially the same arrangement as in 2 establish loose axial Cu···Cl interactions, each one of them with the Cl atom of the other one. Compounds 1 and 2 have been tested as reversible trapping agents for the controlled radical polymerization of styrene under a reverse atom‐transfer radical polymerization (ATRP) approach. Reversible Cl atom transfer leading to a controlled polymerization process is observed, although the controllability is negatively affected by slow radical trapping. A moderate effect on the polymerization rate, once all the radical initiator is consumed, was observed in the presence of an excess amount of pyridine (10 equiv. per Cu) and interpreted on the basis of the stabilization of the CuI system.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

2011

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“…For the conformations of -ketoamines, see: Pastrá n et al (2011); Zharkova et al (2009). For reactions involving aminoketonate complexes, see: He et al (2003); Hsu, Chang et al (2004); Lai et al (2005); Li et al (2005); Tang et al (2005); Hsu, Li et al (2007); Pan et al (2008). For the preparation and coordination chemistry of aminoketonate ligands, see: Jones et al (1998); Shukla et al (2005); Lesikar et al (2008); Sedai et al (2008).…”

Section: Related Literaturementioning

confidence: 99%

“…Anions of β-amino-α-enones are potentially useful bidentate ligands (Jones, et al, 1998;Shukla, et al, 2005;Hsu, Li et al, 2007;Lesikar, et al, 2008;Sedai, et al, 2008) in stoichiometric (Hsu, Chang et al, 2004) and catalytic processes (He, et al, 2003;Lai, et al, 2005;Li, et al, 2005;Tang, et al, 2005;Pan, et al, 2008). Generally, β-amino-α-enones have Z conformations that are stabilized by intramolecular hydrogen bonds (Zharkova, et al, 2009;Pastrán et al, 2011).…”

Section: S1 Commentmentioning

confidence: 99%

(Z)-4-(2,5-Di-tert-butylanilino)pent-3-en-2-one

et al. 2011

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In the crystal structure of the title ketoamine, C19H29NO, the bond lengths from the N atom through the alkene group to the ketone O atom show the presence of an extensively delocalized π-system. The dihedral angle between the plane of the phenyl ring and that of the alkene component is 63.45 (7)° due to steric hindrance exerted by the tert-butyl groups. The molecule has a Z-configured alkene function, which is facilitated by an intramolecular N—H⋯O hydrogen bond between the amine and ketone groups. The molecules are linked into extended chains, which run parallel to the [010] direction, by a very weak C—H⋯O interaction between the methyl substituent of the alkene group and the ketone O atom of a neighbouring molecule.

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“…For chiral camphor-derived -aminoketonate ligands, see: Everett & Powers (1970); Casella et al (1979). For reactions involving aminoketonate complexes, see: Hsu, Chang et al (2004); Hsu, Li et al (2007); Lai et al (2005); Pan et al (2008); Wang et al (2006). For the coordination chemistry of -aminoketonate ligands, see: Lesikar et al (2008); Sedai et al (2008).…”

Section: Related Literaturementioning

confidence: 99%

(E)-3-(1-Naphthylamino)methylene-(+)-camphor

et al. 2010

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In the crystal structure of the title ketoamine {systematic name: (E)-1,7,7-trimethyl-3-[(1-naphthylamino)methylidene]bicyclo[2.2.1]heptan-2-one}, C21H23NO, there are two independent molecules in the asymmetric unit. Both molecules have an E configuration about the alkene function. The main conformational difference between the molecules is in the orientation of the plane of the naphthyl rings with respect to the camphor fragment. The torsion angle about the enamine C—N bond is 21.3 (7)° for molecule A, but −24.4 (8)° for molecule B. Intermolecular N—H⋯O hydrogen bonds between the amino and ketone groups of adjacent independent molecules sustain the crystal, and the resulting extended chains, containing an alternating sequence of the two independent molecules, run parallel to the [001] direction and can be described by a graph-set motif of C 2 2(12).

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Synthesis and characterization of Cu(I) and Cu(II) complexes containing ketiminate ligands

Cited by 16 publications

References 44 publications

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

Synthesis and Structure of Four‐Coordinate Copper(II) Complexes Stabilized by β‐Ketiminato Ligands and Application in the Reverse Atom‐Transfer Radical Polymerization of Styrene

(Z)-4-(2,5-Di-tert-butylanilino)pent-3-en-2-one

(E)-3-(1-Naphthylamino)methylene-(+)-camphor

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