Iminoacylation

Metal-mediated hydrolysis of the oxime CN bond to produce RhIII-bound O-iminoacylated MeC(NH)ONH2 species

“…Thus, Wieghardt et al 8 discovered the addition of monomethylhydroxylamine via N to MeCN in a molybdenumpromoted reaction, while McDonell et al 9 observed dealkylation of Et 2 NOH followed by the addition at N of acetonitrile in a tungsten-mediated process. In contrast to these observations, indicating the high nucleophilic affinity of the N atom of the substituted hydroxylamines, we recently observed additions at O of R 2 NOH to MeCN bound to platinum() ion, 10 which proceed similarly to reactions of nitrile metal compounds with oximes described recently by us. 11- 15 It is worthwhile to mention that our attempts to react unsubstituted NH 2 OH with nitriles bound to Pt IV , Pt II , Re IV and Rh III failed due to both reduction of the metal centres and some other uncontrolled processes that accompanied the interaction.…”

Preparation of Hydroxylamine Complexes of Ruthenium(II), Osmium(II) and Iridium(III)

“…The attack of the oxygen atom of the hydroxylamine in these reactions is rather surprising, since the reaction with free nitriles involves, in the majority of cases, N‐addition 13−15. An O‐addition has been reported16 in the reaction of the platinum complex [PtCl 4 (CH 3 CN) 2 ] with N ‐substituted hydroxylamine R 2 NOH, but the steric hindrance at the N‐atom makes the O‐attack plausible in this case. This is the only known example16 of the reaction of a substituted hydroxylamine with coordinated RCN.…”

“…An O‐addition has been reported16 in the reaction of the platinum complex [PtCl 4 (CH 3 CN) 2 ] with N ‐substituted hydroxylamine R 2 NOH, but the steric hindrance at the N‐atom makes the O‐attack plausible in this case. This is the only known example16 of the reaction of a substituted hydroxylamine with coordinated RCN. In our [M(RCN) 2 P 4 ] 2+ complexes the coordination of the nitrile to the MP 4 fragment probably makes the nitrile carbon increasingly susceptible to nucleophilic attack by the more electronegative oxygen, yielding the O ‐iminoacylated derivatives.…”

trans-Tetrachlorobis[(E)-ethyl 2-(1-iminopropoxyimino)propanoate]platinum(IV)

“…In the course of our study of the reactivity of metal-activated nitriles toward nucleophilic addition Bokach & Kukushkin, 2005), we have observed coupling between nitriles in (RCN) [M] (M = Pt IV , Pt II , Rh III or Re IV ) complexes and HON nucleophiles such as 'simple' oximes (Kukushkin et al, 1998;Kuznetsov et al, 2000), vic-dioximes (Kukushkin et al, 2000), oximehydrazones (Garnovskii et al, 2004), dialkyl hydroxylamines (Wagner et al, 1999;Luzyanin et al, 2005) and hydroxamic acids (Luzyanin et al, 2002(Luzyanin et al, , 2004. The reactions lead to the formation of species with new C-O{N} bonds upon addition of the OH group to the C N moiety of metalactivated nitriles, RCN.…”