The new copper(I) nitro complex [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))] (2), containing the anionic hydrotris(3,5-dimethylpyrazolyl)borate ligand, was synthesized, and its structural features were probed using X-ray crystallography. Complex 2 was found to cocrystallize with a water molecule, and X-ray crystallographic analysis showed that the resulting molecule had the structure [(Ph(3)P)(2)N][Cu(HB(3,5-Me(2)Pz)(3))(NO(2))]·H(2)O (3), containing a water hydrogen bonded to an oxygen of the nitrite moiety. This complex represents the first example in the solid state of an analogue of the nitrous acid intermediate (CuNO(2)H). A comparison of the nitrite reduction reactivity of the electron-rich ligand containing the CuNO(2) complex 2 with that of the known neutral ligand containing the CuNO(2) complex [Cu(HC(3,5-Me(2)Pz)(3))(NO(2))] (1) shows that reactivity is significantly influenced by the electron density around the copper and nitrite centers. The detailed mechanisms of nitrite reduction reactions of 1 and 2 with acetic acid were explored by using density functional theory calculations. Overall, the results of this effort show that synthetic models, based on neutral HC(3,5-Me(2)Pz)(3) and anionic [HB(3,5-Me(2)Pz)(3)](-) ligands, mimic the electronic influence of (His)(3) ligands in the environment of the type II copper center of copper nitrite reductases (Cu-NIRs).
Supporting Information Supporting Information Available: Compound characterization data, including NMR spectra, details of the kinetic study, and DFT atom coordinates and absolute energies for all relevant computationally studied species. This material is available free of charge via the Internet.
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).
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.