title: Characterization of a new copper(I)-nitrito complex that evolves nitric oxide.
abstract: The complexes [Cu(kappa(2)-Ph(2)PC(6)H(4)(o-OMe))(2)(CH(3)CN)](BF(4)) (1) and [CuCl(Ph(2)PC(6)H(4)(o-OMe))(2)] (2) have been prepared by treating [Cu(CH(3)CN)(4)](BF(4)) or CuCl with two equivalents o-(diphenylphosphino)anisole (Ph(2)PC(6)H(4)(o-OMe)) at room temperature, respectively. The reaction of 1 and (PPN)(NO(2)) in acetonitrile solution affords a neutral compound [Cu(Ph(2)PC(6)H(4)(o-OMe))(2)(ONO)] (3). In contrast to the synthesis of 3, mixing NaNO(2) and 1 in MeOH yielded a unique dicopper(I) cationic species, [((Ph(2)PC(6)H(4)(o-OMe))(2)Cu)(2)(mu-NO(2))](+) (4) after ether/CH(2)Cl(2) crystallization. The molecular structures of 1-4 have been determined by an X-ray diffraction study. The copper(I)-nitrito adduct 3 containing phosphine-ether ligands forms nitric oxide gas from the reaction with acetic acid, suggesting the first example and model compound in the asymmetric O-bound copper(I) nitrite intermediate microenvironment of copper nitrite reductases (Cu-NIRs).
authors.affiliation: Department of Medicinal and Applied Chemistry and Center of Excellence for Environmental Medicine, Kaohsiung Medical University, Kaohsiung 807, Taiwan.
authors.forename: Wan-Jung
authors.initials: WJ
authors.lastname: Chuang
authors.forename: I-Jung
authors.initials: IJ
authors.lastname: Lin
authors.forename: Hsing-Yin
authors.initials: HY
authors.lastname: Chen
authors.forename: Yu-Lun
authors.initials: YL
authors.lastname: Chang
authors.forename: Sodio C N
authors.initials: SC
authors.lastname: Hsu
mesh_terms: D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D003460:Crystallization; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009572:Nitrite Reductases / Q000737:chemistry / Q000378:metabolism; D009574:Nitro Compounds / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D008024:Ligands; D009574:Nitro Compounds; D009589:Nitrogen Oxides; D009942:Organometallic Compounds; D003300:Copper; D009572:Nitrite Reductases; C052695:nitrite reductase, copper-containing