1-4-7-trimethyl-1-4-7-triazacyclononane and 1-4-7-triazacyclononane

A novel dicyanoosmium(III) complex, trans-Ph(4)P[Os(III)(salen)(CN)(2)].CH(2)Cl(2).H(2)O (1; Ph(4)P(+) = tetraphenylphosphonium cation, salen(2-) = N,N'-ethylenebis(salicylideneaminato) dianion), has been synthesized and structurally characterized. Reactions of 1 with [Cu(Me(3)tacn)(H(2)O)(2)](ClO(4))(2) (Me(3)tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) under different conditions produce the 1-D ferromagnetic zigzag chains [Os(salen)(CN)(2)](2)[Cu(Me(3)tacn)].CH(3)OH (2) and [Os(salen)(CN)(2)][Cu(Me(3)tacn)].ClO(4) (3).

Topics: Aza Compounds; Catalysis; Crystallography, X-Ray; Drug Design; Ethylenediamines; Ferric Compounds; Heterocyclic Compounds; Hydrogen Peroxide; Kinetics; Magnetics; Models, Chemical; Molecular Structure; Piperidines; Spectroscopy, Fourier Transform Infrared; Thermodynamics

The gas-phase reactions of a series of (di)manganese carbonyl positive ions with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me(3)TACN) have been examined with the aid of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry. The monomanganese carbonyl ions, [Mn(CO)(n)](+) (n = 2-5), react predominantly by ligand exchange and to a minor extent by electron transfer with the formation of the radical cation of Me(3)TACN. For the [Mn(CO)(n)](+) (n = 2-4) ions, the ligand exchange results in the exclusive formation of a [Mn(Me(3)TACN)](+) complex, whereas small amounts of [Mn(CO)(Me(3)TACN)](+) ions are also generated in the reactions of the [Mn(CO)(5)](+) ion. The [Mn(2)(CO)(n)](+) ions (n = 2, 4 and 5) react also by competing electron transfer and ligand exchange. The reaction of the [Mn(2)(CO)(2)](+) and [Mn(2)(CO)(4)](+) ions is associated with cleavage of the Mn--Mn bond as evidenced by the pronounced formation of [Mn(Me(3)TACN)](+) ions. For [Mn(2)(CO)(5)](+), the ligand exchange leads mainly to the formation of [Mn(2)(CO)(n)(Me(3)TACN)](+) (n = 1-3) ions. These primary product ions react subsequently by the incorporation of a second Me(3)TACN molecule to afford [Mn(2)(CO)(Me(3)TACN)(2)](+) and [Mn(2)(CO)(2)(Me(3)TACN)(2)](+) ions. Both of these latter species incorporate an oxygen molecule with formation of ions with the assigned composition of [Mn(2)(O(2))(CO)(Me(3)TACN)(2)](+) and [Mn(2)(O(2))(CO)(2)(Me(3)TACN)(2)](+).

Topics: Aza Compounds; Heterocyclic Compounds; Manganese Compounds; Organometallic Compounds; Spectroscopy, Fourier Transform Infrared