Abstract
According to spectrophotometric data, the reaction of trans-[Ru(NH 3) 4P(OEt) 3(H 2O)] 2+ with NO 2 - in alkaline medium ( C H + < 10 - 9 mol L - 1 ) occurs on two steps. In the first, both the nitro ( trans-[Ru(NH 3) 4P(OEt) 3(NO 2)] +) and nitrito ( trans-[Ru(NH 3) 4P(OEt) 3(ONO)] +) isomers are formed. In the second step, the nitrito isomer is converted into the nitro form. Under equilibrium conditions and using pyrazine as auxiliary ligand, the formation constant, K N, of trans-[Ru(NH 3) 4P(OEt) 3(NO 2)] + (5.2 ± 0.6) × 10 3 M −1 (pH 11.0; μ = 0.3 mol L −1 NaCF 3COO; T = (25 ± 0.2) °C) was measured using the Indicator Colorimetric Method. The spectrophotometrically measured specific rate constant for the equation of the nitrite ligand in trans-[Ru(NH 3) 4P(OEt) 3(NO 2)] +, was (1.2 ± 0.3) × 10 −1 s −1(pH 10.9; μ = 0.3 mol L −1 NaCF 3COO; T = (25 ± 0.2) °C). Trans-[Ru(NH 3) 4P(OEt) 3NO 2] + was quantitatively converted into the trans-[Ru(NH 3) 4P(OEt) 3NO] 3+ in acid solutions ( C H + > 10 - 5 mol L - 1 ; k obs = 2.2 × 10 −3 s −1 at pH 4). However the inverse conversion was not quantitative.
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