Formation of a chelating bidentate nitrosoalkane complex of ruthenium(II) through reaction of H₂O with a high-valent bis(imido)ruthenium intermediate and X-ray crystal structure of [Ru(bpy)₂(ONCMe₂CMe₂NO)][ClO₄]₂·Me₂CO

Abstract

Oxidation of [ R U ~~( ~~~) ~( N H ~C M ~~C M ~~N H ~) ~~+ by Celv in H20 generates the highly reactive cis-b i s ( i m i d o ruth e n i u m (vi 1 i n t e r m ed i ate , w h i c h re acts with H 0 to g ive [ R u 11 ( b py ) ( 0 N C M e2 C M e2 N 0 ) 12+, t h e structure of which has been determined by X-ray crystallography.

Terminal Nitrido and Imido Complexes of the Late Transition Metals

“…[172] Ruthenium imido=nitrene complexes with structure types V or VI have also been proposed in several instances but not isolated. [173][174][175][176][177][178] Osmium imido species with structure V have been prepared from the corresponding Os(VI)-nitrido species; an example with Os in each of the three oxidation states Os(IV), Os(V), and Os(VI) is known. The Os(IV) complex, [(tpy)(bpy)Os=NÀNEt 2 ] 2+ , has been characterized by X-ray crystallography.…”

Density Functional Theory Calculations on Oxidative CC Bond Cleavage and NO Bond Formation of [RuII(bpy)2(diamine)]2+ via Reactive Ruthenium Imide Intermediates

“…On the basis of the DFT studies in this work together with recent findings by Sakai and co‐workers on the nature of ammonium cerium(IV) nitrate in water,32 useful insights can be gained into the mechanism of the oxidation of M1 by ammonium cerium(IV) nitrate in aqueous CF 3 COOH solution (a proposed pathway is depicted in Scheme ). As this reaction gave the NO bond formation product M4 in 70 % isolated yield,19b, 21 the pathway featuring water nucleophilic attack on A′ is unlikely to play a major role owing to its substantially higher activation free energy than that of the CC bond cleavage of A′ (see above). If ammonium cerium(IV) nitrate is used as oxidant, there could be other species (besides water molecules) that could attack the imide group.…”

“…The following complexes were employed for the DFT calculations in this work (see Figure 2): i) ruthenium diamine complexes [Ru II (bpy)(tmen)] 2+ ( M1 )18 and [Ru II (bpy) 2 (heda)] 2+ ( M2 , heda=2,5‐dimethyl‐2,5‐hexanediamine);21 ii) products [Ru II (bpy) 2 (NH=CMe 2 ) 2 ] 2+[18] ( M3 ) and [Ru II (bpy) 2 (ONCMe 2 CMe 2 NO)] 2+[19b] ( M4 ) in the electrochemical oxidation and Ce IV oxidation of M1 , respectively; iii) [Ru(bpy) 2 (tmen‐4 H)] + ( A ), [Ru(bpy) 2 (tmen‐3 H)] 2+ ( A′ ), and [Ru(bpy) 2 (tmen‐4 H)] 2+ ( A“ ), as the proposed Ru V ‐bis(imide), Ru V ‐imide/amide,18 and Ru VI ‐bis(imide)19b intermediates, respectively (Figure 2), from oxidative deprotonation of M1 ; iv) [Ru(bpy) 2 (heda‐3 H)] 2+ ( M5 ) as the proposed Ru V ‐imide/amide intermediate from oxidative deprotonation of M2 ; v) product [Ru II (bpy) 2 (NHCMe 2 )(MeCN)] 2+[21] ( M6 ) generated in the oxidation of M1 with bromine in acetonitrile. Details of the optimized structures and comparison with the X‐ray crystal structures are shown in the Supporting Information (see Figure S1 and Table S1); the absorption spectra of M1 and M4 obtained through time‐dependent DFT (TD‐DFT) calculations (Figures S2 and S3, Tables S2–S5, Supporting Information) are also given together with the experimental spectra.…”

“…Interestingly, with ammonium cerium(IV) nitrate as oxidant, the NO bond formation of M1 to give [Ru II (bpy) 2 (ONCMe 2 CMe 2 NO)] 2+ ( M4 ) was observed 19b. 21 This reaction creates a precedent for direct oxidation of the coordinated diamine (tmen) in metal‐tmen complexes to dinitrosoalkane.…”

活性钌、锇-配体多重键配合物研究进展

“…[84] . 这 是自从Groves等报道氮合锰(V)卟啉 [90] 及Carreira [91] 和Komatsu [92] [96,97] , 这些物种可被看作是金属催化硝酸盐 和氨之间氧化还原相互转换过程中的关键活性中间 体.…”