Synthesis, Characterization, and Molecular Structures of Diethylnitrosamine Metalloporphyrin Complexes of Iron, Ruthenium, and Osmium.

Diethylnitrosamine reacts with [(TPP)Fe(THF)(2)]ClO(4) (TPP = 5,10,15,20-tetraphenylporphyrinato dianion) in toluene to generate the bis-nitrosamine complex, [(TPP)Fe(Et(2)NNO)(2)]ClO(4), in 96% isolated yield. The related [(TTP)Fe(Et(2)NNO)(2)]SbF(6) (TTP = 5,10,15,20-tetra-p-tolylporphyrinato dianion) complex is prepared in 70% isolated yield via a similar reaction in CH(2)Cl(2). Reaction of [(TPP)Fe(Et(2)NNO)(2)]ClO(4) in CH(2)Cl(2) with NO gas results in the displacement of one of the Et(2)NNO ligands to give the air-sensitive and thermally sensitive [(TPP)Fe(NO)(Et(2)NNO)]ClO(4) derivative. Reaction of (OEP)Ru(CO) (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato dianion) with NOBF(4) in CH(2)Cl(2) gives [(OEP)Ru(NO)(H(2)O)]BF(4) as the final isolated product (after exposure to air) in 71% isolated yield. The aqua ligand is then displaced by Et(2)NNO in CH(2)Cl(2) to give [(OEP)Ru(NO)(Et(2)NNO)]BF(4) in 82% isolated yield. The valence isoelectronic (OEP)Ru(CO)(Et(2)NNO) compound is prepared in 71% isolated yield by the addition of excess Et(2)NNO to (OEP)Ru(CO) in CH(2)Cl(2). The nitrosyl amine complex [(OEP)Ru(NO)(HNEt(2))]BF(4) is prepared (i) in 78% yield by diethylamine addition to [(OEP)Ru(NO)(H(2)O)]BF(4) or (ii) in 71% isolated yield by diethylamine addition to [(OEP)Ru(NO)(Et(2)NNO)]BF(4). The osmium nitrosamine complexes, (TTP)Os(CO)(Et(2)NNO) and (OEP)Os(CO)(Et(2)NNO), are prepared in 74% and 66% yields, respectively, by diethylnitrosamine addition to the precursor (porphyrin)Os(CO) compounds in CH(2)Cl(2). The nitrosyl [(OEP)Os(NO)(Et(2)NNO)]BF(4) derivative is prepared in quantitative yield (by IR and (1)H NMR spectroscopy) by the reaction of (OEP)Os(CO)(Et(2)NNO) with NOBF(4). Labeling studies using (15)NOBF(4), Et(2)N(15)NO, and Et(2)NN(18)O have been used to assign the nitrosyl and nitrosamine bands in the IR spectra of several of the complexes. The solid-state structures of [(TPP)Fe(THF)(2)]ClO(4), [(TPP)Fe(Et(2)NNO)(2)]ClO(4), [(OEP)Ru(NO)(H(2)O)]BF(4), (OEP)Ru(CO)(Et(2)NNO), and (TTP)Os(CO)(Et(2)NNO) have also been determined by single-crystal X-ray diffraction. The Et(2)NNO ligands display a rare eta(1)-O binding mode in all three nitrosamine complexes.