Chapter 4 of this dissertation deals with the first isolable nitrone adducts of metalloporphyrins. Thus, the metalloporphyrin nitrone complexes (OEP)M(CO)(DMPO) (M = Ru, Os; DMPO = 5,5-dimethyl-1-pyrroline N-oxide) were prepared in 61--75%, isolated yields from the reaction of (OEP)M(CO) with excess DMPO.

Chapter 5 of this dissertation deals with the examination of the binding of nitrosoarenes, pyridine, and 1-methylimidazole (1-MeIm) to ruthenium porphyrins. Thus, a series of the (por)Ru(ArNO)2 (por = TPP, TTP; ArNO = PhNO, o-tolNO, N(O)-C6H4OMe-p, N(O)C 6H2(Me)2OMe-p) complexes were prepared in 49--75% isolated yields from the reaction of (por)Ru(CO) with excess ArNO.

Chapter 1 of this dissertation introduces the fundamental issues involved in the chemistry and biochemistry of organic S- and C-nitroso compounds. Thus, the syntheses and properties of organic S- and C-nitroso compounds, and their reactions with heme and heme models are reviewed in Chapter 1.

Chapter 3 of this dissertation describes the syntheses of the monometallic nitrosyl thiolate-thiol complexes and their novel bimetallic mu-dithiolate derivatives by using an alkoxide-thiolate exchange method or the formal trans-addition of RSNO. Thus, the monometallic nitrosyl thiolate-thiol complexes of the form (por)Ru(NO)(S(CH2)nSH) (por = TPP, n = 2; TTP, n = 3--4) were prepared in 49--58% isolated yields from the reaction of the (por)Ru(NO)(O- i-C5H11) alkoxide precursors with HS(CH 2)nSH in CH2Cl2.

Chapter 2 of this dissertation describes the syntheses of the (OEP)Os(NO)(SR) compounds via the addition of RSNO to (OEP)Os(CO) or via an alkoxide-thiolate exchange reaction. Thus, the (OEP)Os(NO)(SR) compounds (R = Me, Et, iPr, tBu) were prepared in 33--48% isolated yields by the formal trans-addition of the precursor thionitrites (RSNO) across the metal center in (OEP)Os(CO).

This dissertation deals with the interactions of organic S-nitroso (RS-N=0) and C-nitroso (C-N=0) compounds with ruthenium and osmium porphyrins.