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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.

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for their support and advice. My special thanks go to Professor Stanley C. Neely, who interviewed me in Sri Lanka and encouraged me to enter to the graduate program at University of Oklahoma. He has been both a friend and a Professor to me during my graduate studies. I wish to give my sincere thanks to Mrs. Christian and Professor Christian, for the kindness given to me and my family by sending cards and giving gifts to my little two daughters on various occasions. q I should be very thankful to the Department of Chemistry and Biochemistry of ' University of Oklahoma for the funding made available to me by providing a graduate assistantship. I also appreciate financial support provided by the National Science