Characterization of a new copper(I)-nitrito complex that evolves nitric oxide.
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).
Chuang
Wan-Jung
WJ
Department of Medicinal and Applied Chemistry and Center of Excellence for Environmental Medicine, Kaohsiung Medical University, Kaohsiung 807, Taiwan.
Lin
I-Jung
IJ
Chen
Hsing-Yin
HY
Chang
Yu-Lun
YL
Hsu
Sodio C N
SC
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
D008024:Ligands; D009574:Nitro Compounds; D009589:Nitrogen Oxides; D009942:Organometallic Compounds; D003300:Copper; D009572:Nitrite Reductases; C052695:nitrite reductase, copper-containing