Abstract
N,O-chelating dicarbonylhydrazido-palladium complexes were synthesized by treatment of 1,2-bis(trifluoroacetyl)hydrazine with a mixture of a Pd(0) source, [Pd(dba)2] (DBA = dibenzylideneacetone), and four-electron donors including 1,3-bis(diphenylphosphino)propane (DPPP), N,N,N’,N’-tetramethylethylenediamine (TMEDA), and two equivalents of triphenylphosphine. The same products from DPPP and TMEDA could be obtained alternatively by using Pd(OAc)2 through deprotonation of the diacylhydrazine. The five-membered chelate structure was confirmed by NMR spectra and X-ray crystal structure determination. The X-ray structures indicate that the products are formally considered as Pd(II) complexes with a hydrazido(2–) ligand. In the case of the triphenylphosphine-coordinated complex, a fluxional behavior in dichloromethane-d2 was observed by variable temperature NMR experiments, possibly due to structural changes between the square planar and pseudo-tetrahedral geometries.
Highlights
N,O-chelating dicarbonylhydrazido-palladium complexes were synthesized by treatment of 1,2-bis(trifluoroacetyl)hydrazine with a mixture of a Pd(0) source, [Pd(dba)2 ] (DBA = dibenzylideneacetone), and four-electron donors including 1,3-bis(diphenylphosphino)propane (DPPP), N,N,N 0,N 0 -tetramethylethylenediamine (TMEDA), and two equivalents of triphenylphosphine
In light of reductive N–N bond transformations promoted by carbonyl functional groups [6,7,8], acylhydrazines are expected to be eligible for oxidative addition
Inorganics 2021, 9, 76 luminescence application of dinuclear complexes connected by a diacylhydrazido bridge bridge [21,22], the diacylhydrazine framework has been utilized as a substructure of
Summary
The N–N bond scission has not been observed for low-valent late transition metal complexes [9] with the exception of a highly strained hydrazine analog, di-tert-butyldiaziridinone, convertible to a four-membered oxidative addition product by Pd(0) species [10]. In the context of of these attractive aspects, we turned our attention to an activated hydrazine molecule, these attractive aspects, we turned our attention to an activated hydrazine molecule, 1,21,2-bis(trifluoroacetyl)hydrazine (1), in which two strongly electron-withdrawing carbonyl bis(trifluoroacetyl)hydrazine (1), in which two strongly electron-withdrawing carbonyl groups were expected to facilitate N–N and N–H bond transformations [29]. We disclose the reactivity of 1 towards Pd(0) species, in conjunction with its deprotonative disclose the reactivity of 1 towards Pd(0) species, in conjunction with its deprotonative coordination toward Pd(II) variants
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