Abstract
The synthesis, characterization and reactivity of trans - [ Ru ( NH 3 ) 4 P ( OEt ) 3 NO ] X 3 ( X = PF 6 - and CF 3 COO - ) are presented. The X-ray structure of trans-[Ru(NH 3) 4P(OEt) 3NO](CF 3COO) 3 · 3CF 3COOH indicates coordination of the nitrosyl as NO with a Ru–N–O angle of 175.1(8)° and a Ru–NO bond length of 1.774(8) Å. Loss of NO 2 - from trans-[Ru(NH 3) 4P(OEt) 3NO] 3+ is pH dependent with k obs (s −1) = ( k 0 K a + k 1[H +])/([H +] + K a)], where k 0 = 2 × 10 −5 s −1, k 1 = 0.40 ± 0.03 s −1, and p K a = 8.6 ± 0.3. The nitrosyl complex undergoes a one-electron reduction ( E 0 = 0.14 V versus NHE) involving the coordinated nitrosyl group followed by dissociation of NO, which is facilitated by the phosphito ligand ( k −NO = 0.97 s −1 at 25 °C and pH 5.0).
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