title: Reactivity Study of Unsymmetrical β-Diketiminato Copper(I) Complexes: Effect of the Chelating Ring.
abstract: β-Diketiminato copper(I) complexes play important roles in bioinspired catalytic chemistry and in applications to the materials industry. However, it has been observed that these complexes are very susceptible to disproportionation. Coordinating solvents or Lewis bases are typically used to prevent disproportionation and to block the coordination sites of the copper(I) center from further decomposition. Here, we incorporate this coordination protection directly into the molecule in order to increase the stability and reactivity of these complexes and to discover new copper(I) binding motifs. Here we describe the synthesis, structural characterization, and reactivity of a series of unsymmetrical N-aryl-N'-alkylpyridyl β-diketiminato copper(I) complexes and discuss the structures and reactivity of these complexes with respect to the length of the pyridyl arm. All of the aforementioned unsymmetrical ß-diketiminato copper(I) complexes bind CO reversibly and are stable to disproportionation. The binding ability of CO and the rate of pyridyl ligand decoordination of these copper(I) complexes are directly related to the competition between the degree of puckering of the chelate system and the steric demands of the N-aryl substituent.
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Wan-Jung
authors.initials: WJ
authors.lastname: Chuang
authors.affiliation: Department of Physiology, School of Medicine, College of Medicine, Taipei Medical University , Taipei 110, Taiwan.|Graduate Institute of Medical Sciences, College of Medicine, Taipei Medical University , Taipei 110, Taiwan.
authors.forename: Sung-Po
authors.initials: SP
authors.lastname: Hsu
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Kuldeep
authors.initials: K
authors.lastname: Chand
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Fu-Lun
authors.initials: FL
authors.lastname: Yu
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Cheng-Long
authors.initials: CL
authors.lastname: Tsai
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Yu-Hsuan
authors.initials: YH
authors.lastname: Tseng
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Yuh-Hsiu
authors.initials: YH
authors.lastname: Lu
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Jen-Yu
authors.initials: JY
authors.lastname: Kuo
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.|Department of Applied Chemistry, National University of Kaohsiung , Kaohsiung 804, Taiwan.
authors.forename: James R
authors.initials: JR
authors.lastname: Carey
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Hsuan-Ying
authors.initials: HY
authors.lastname: Chen
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Hsing-Yin
authors.initials: HY
authors.lastname: Chen
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.|Department of Chemistry, National Sun Yat-Sen University , Kaohsiung 804, Taiwan.
authors.forename: Michael Y
authors.initials: MY
authors.lastname: Chiang
authors.affiliation: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University , Kaohsiung 807, Taiwan.|Department of Medical Research, Kaohsiung Medical University Hospital , Kaohsiung 807, Taiwan.
authors.forename: Sodio C N
authors.identifier: http://orcid.org/0000-0002-2576-7289
authors.initials: SC
authors.lastname: Hsu