ONE-ELECTRON OXIDATION BEHAVIOR OF (MNO)(6)-TYPE NITROSYL COMPLEXES HAVING ACETYLACETONATO LIGAND, [M(NO)CL5-2N(ACAC)(N)](M) (M=RU, OS N=1,2 ACAC EQUALS ACETYLACETONATO)

The electrochemical behavior of several complexes with the general for mula [M(NO)Cl5-2n(acac)(n)](m) (M=Ru, Os; n=1, 2; acac=acetylacetonato ) was investigated: mer-[Ru(NO)Cl-3(acac)](-)(1, n=1), cis-[Ru(NO)Cl(a cac)(2)] (2, n=2), mer-[Os(NO)Cl-3(acac)](-) (3, n=1), cis-[Os(NO)CI(a cac)(2)] (4, n=2). The study includes the known corresponding n=0 comp lexes, [M(NO)Cl-5](2-) (M=Ru, Os), for comparison. All these complexes undergo a one-electron oxidation, which is rather unusual redox behav ior in the {MNO}(6)-type nitrosyl complexes. The behavior of some of t hese complexes as electrophiles was also described. Molecular structur es with a meridional configuration were established for the n=1 comple xes ([Ru(NO)Cl-3(acac)](-) (1) and [Os(NO)Cl-3(acac)](-) (3)) by X-ray structure determinations. Crystal data for 1 (Bu4N salt): C21H43N2O3C l3Ru, a=31.443(9), b=21.86(1), c=19.852(6) Angstrom, beta=119.65(2)deg rees, monoclinic, C2/c, Z=16. Crystal data for 3 (Cs salt): C5H7NO3Cl3 OsCs, a=7.942(1), b=12.602(2), c=7.451(2) Angstrom, alpha=105.91(2), b eta=98.20(2), gamma=90.31(1)degrees, triclinic, P (1) over bar, Z=2.