Mechanistic aspects of the reactions of nitric oxide with transition-metal complexes.

Transition metal nitrite complexes

The synthesis, X-ray crystal structures, and some spectroscopic and chemical properties of the nitrosylruthenium(II) porphyrin complexes Ru(TPP)(NO)(ONO), Ru(TPP)(NO)(OH), Ru(OEP)(NO)(ONO), and Ru(OEP)(NO)(OH) (TPP = tetraphenylporphyrinato dianion; OEP = octaethylporphyrinato dianion) derived from the analogous Ru(II) carbonyl complexes are reported. Also described are experiments which quantitatively demonstrate that N2O is formed as a product of the synthesis scheme and that NO serves as the principal oxidant in the transformation of N(II) to N(III). The two TPP complexes are isostructural and consist of columns of molecules stacked along the c axis. The two OEP complexes are also isostructural and can be considered as layers of OEP complexes stacked along the b axis with solvent molecules situated at the cavities between layers. The nitrite ions are coordinated in a unidentate fashion through the oxygen atom. Crystal data for Ru(TPP)(NO)(ONO) (1):  M = 789.79, space group I4/m (No. 87), a = 13.6529(6)...

Synthesis and Structural Characterization of Several Ruthenium Porphyrin Nitrosyl Complexes

The reaction of the iron(II) picket fence porphyrin derivative [Fe(TpivPP)(NO2)]- (Nasri et al. J. Am. Chem. Soc. 1991, 113, 717) with NO has been examined. The result is a new hexacoordinated iron...

Sharing the π-Bonding. An Iron Porphyrin Derivative with Trans, π-Accepting Axial Ligands. Synthesis, EPR and Mössbauer Spectra, and Molecular Structure of Two Forms of the Complex Nitronitrosyl(α,α,α,α-tetrakis(o-pivalamidophenyl)- porphinato)ferrate(II)

(Nitrosyl)(salen)ruthenium(II) complex 1 was found to serve as an efficient catalyst for the epoxidation of conjugated olefins under photoirradiation, with 2,6-dichloropyridine N-oxide (2) or tetramethylpyrazine N,N'-dioxide as a stoichiometric oxidant. High enantioselectivity was achieved irrespective of the substitution pattern of olefins. The choice of solvent depends on stability of the resulting epoxides: high enantioselectivity is generally observed in the reaction with ethereal solvents, but use of benzene is recommended when the resulting epoxides are acid-sensitive.

J. R. Thornback

Papers

An o-bonded nitrito nitrosyl schiff base complex: X-ray molecular structure of [Ru(sal2en)(NO2)(NO)]

An O-Bonded Nitrito Nitrosyl Schiff Base Complex: X-Ray Molecular Structure of [Ru(sa12en)(NO, )(NO)] (Hzsalgen: N,NiÄthylen-bis-[salicylidenamin].