Journal of the Chemical Society, Dalton Transactions p. 2737 - 2740 (1987)
Update date:2022-08-04
Topics:
Connelly, Neil G.
Garcia, Gabriel
The complex ((Ir(μ-Cl)(η4-cod))2) (cod= cyclo-octa-1,5-diene) reacts with the triazene RNNNHR (R=p-tolyl) to give (IrCl(RNNNHR)(η4-cod)) (1) which yields (IrCl(CO)2(RNNNHR)) (2) on treatment with CO gas.Deprotonation of (2) with NEt3 in CH2Cl2 at -10 deg C gives the dimer ((Ir(CO)2(μ-RNNNR))2) (3), which undergoes thermal substitution with PPh3 to yield (Ir(CO)3(PPh3)(μ-RNNNR)2) (4).Complexes (3) and (4) undergo reversible one-electron oxidation at a platinum electrode in CH2Cl2.In the presence of PPh3, (4) (or (3)) reacts with (Fe(η-C5H5)2)(PF6) to give the isolable paramagnetic salt ((Ir(CO)(PPh3)(μ-RNNNR))2(PF6) which undergoes reversible one-electron reduction and which has been characterised by e.s.r. spectroscopy.
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