Search

The preparation of two RuIII polyaminocarboxylate complexes, AMD6245 and AMD6221, and their nitrosyl analogues, AMD6204, AMD6263, and AMD3689, is described. The compounds are characterized by IR, ES-MS, and 13C and 15N NMR spectroscopy where appropriate and cyclic voltammetry. The crystal structures for AMD6245, AMD6263, and AMD3689 are presented. AMD6245 (C10H14N2O9Ru) crystallized in the P21/c space group with a = 8.4382(2) A, b = 8.8304(2) A, c = 17.6321(4) A, β = 99.603°, V = 1295.3(2) A3, and Z = 4. AMD6263 (C10H14N3O10Ru) crystallized in the P21/c space group with a = 9.9043(4) A, b = 13.1144(3) A, c = 12.0914(4) A, β = 100.191°, V = 1545.8(5) A3, and Z = 4. AMD3689 (C14H24.56N4O13.28Ru) crystallized in the P1 space group with a = 8.838(2) A, b = 9.452(3) A, c = 13.419(4) A, α = 78.413(6)°, β = 75.804(6)°, γ = 73.562(6)°, V = 1031.8(5) A3, and Z = 2. The reaction of AMD6245 and AMD6221 with nitric oxide is investigated using EPR spectroscopy and stopped flow kinetics. Upon reaction with NO, a linea...

The compound 5,17-bis(2-chloroacetamido)-25,26,27,28-tetrapropoxycalix[4]arene, 4, was prepared in the cone conformation by the published method. Compound 4 was reacted with α,α‘-m-xylenedithiol an...

The preparation of a series of [Ru(III)(tacn)(eta(2)-dtc)(eta(1)-dtc)][PF(6)] (tacn = 1,4,7-triazacyclononane; dtc = dimethyldithiocarbamate, diethyldithiocarbamate, pyrrolidinedithiocarbamate, l-prolinedithiocarbamate, l-prolinemethyl ester dithiocarbamate, l-N-methylisoleucinedithiocarbamate) complexes, 5-11, is described. Complex 5 reacts with NO to form the ruthenium nitrosyl complex 12. A series of [Ru(III)(tacn)(pyc)Cl][PF(6)] (pyc = 2-pyridinecarboxylic acid, 2,4- and 2,6-pyridinecarboxylic acid) complexes, 14-16, were prepared along with [Ru(III)(tacn)(mida)][PF(6)] (mida = N-methyliminodiacetic acid), 13, and [Ru(III)(Hnota)Cl], 17, (Hnota = 1-acetic acid-4,7-bismethylcarboxylate-1,4,7-triazacyclononane). Complexes 5-17 were evaluated for use as NO scavengers in an in vitro assay using RAW264 murine macrophage cells. [Ru(III)(tacn)(eta(2)-dtc)(eta(1)-dtc)][PF(6)] complexes 5-11 are very efficient NO scavengers in this assay.

The preparation of two Ru(III) polyaminocarboxylate complexes, AMD6245 and AMD6221, and their nitrosyl analogues, AMD6204, AMD6263, and AMD3689, is described. The compounds are characterized by IR, ES-MS, and (13)C and (15)N NMR spectroscopy where appropriate and cyclic voltammetry. The crystal structures for AMD6245, AMD6263, and AMD3689 are presented. AMD6245 (C(10)H(14)N(2)O(9)Ru) crystallized in the P2(1)/c space group with a = 8.4382(2) A, b = 8.8304(2) A, c = 17.6321(4) A, beta = 99.603(o), V = 1295.3(2) A(3), and Z = 4. AMD6263 (C(10)H(14)N(3)O(10)Ru) crystallized in the P2(1)/c space group with a = 9.9043(4) A, b = 13.1144(3) A, c = 12.0914(4) A, beta = 100.191(o), V = 1545.8(5) A(3), and Z = 4. AMD3689 (C(14)H(24.56)N(4)O(13.28)Ru) crystallized in the P1 space group with a = 8.838(2) A, b = 9.452(3) A, c = 13.419(4) A, alpha = 78.413(6)(o), beta = 75.804(6)(o), gamma = 73.562(6)(o), V = 1031.8(5) A(3), and Z = 2. The reaction of AMD6245 and AMD6221 with nitric oxide is investigated using EPR spectroscopy and stopped flow kinetics. Upon reaction with NO, a linear, diamagnetic [RuNO](6) complex is formed. The substitution reaction of AMD6245 with NO proceeds with a second-order rate constant of 2.24 x 10(7) M(-1) s(-1) at 7.3 degrees C (pH = 7.4; 50 mM phosphate buffer). The substitution reaction of AMD6221 with NO proceeds with a second-order rate constant of 3 x 10(5) M(-1) s(-1) at 20 degrees C (pH = 7.4; 50 mM phosphate buffered saline). The NO scavenging ability was assessed using a RAW264 murine macrophage assay by measuring the difference in nitrite produced between untreated control cells and treated cells. At 100 microM AMD6245 has [NO(2-)] = 12.5 microM less than the untreated cells and AMD6221 has [NO(2-)] = 37.6 microM less than the untreated cells. There is an insignificant difference in the amount of nitrite produced between AMD6263 or AMD3689 treated cells and untreated cells.

Reaction of thiophenol with K[Ru(Hedta)Cl] results in the formation of a bis-thiolato-bridged Ru(III)−Ru(III) dimer (II) possessing a Ru−Ru single bond (2.866(1) A) for which the crystal structure is presented.