Reactivity of a fluorine-containing dirhodium tetracarboxylate compound with proteins

Abstract

Dirhodium complexes of general formula [Rh2(O2CR)4]L2 are a well-known class of bimetallic compounds that are used as efficient catalysts for a variety of reactions and have been shown to be...

Digging into protein metalation differences triggered by fluorine containing-dirhodium tetracarboxylate analogues

“…A summary of the dirhodium ligands and of geometries of the dirhodium compound fragments observed in the present structure(s) is reported in Tables S3 and S4, † compared to the results obtained for the same protein with [Rh 2 (OAc) 4 ] 24,25 and [cis-Rh 2 (OAc) 2 (tfa) 2 ]. 23 Altogether these data support the hypothesis that [Rh 2 (OAc) (tfa) 3 ] can bind proteins at both the equatorial and axial sites, in contrast to [Rh 2 (OAc) 4 ] 24,25 and [cis-Rh 2 (OAc) 2 (tfa) 2 ]. 23…”

“…Far-UV CD spectra of metal-free RNase A and HEWL and the proteins incubated for 24 h with [Rh 2 (OAc)(tfa) 3 ] in a 1 : 3 protein/metal compound molar ratio have a similar shape and compare well with the literature data. 23,25 This finding strongly indicates that the proteins Interaction of [Rh 2 (OAc)(tfa) 3 ] with RNase A…”

“…[Rh 2 (OAc)(tfa) 3 ] was synthesized using a published protocol with slight modifications 23 (experimental details are reported in the ESI †). Precoated silica gel TLC plates (F254, Merck, Darmstadt, Germany) were used to check the progress of the reaction; the exposure of TLC to UV light and iodine vapor was used for monitoring of product formation.…”

“…To synthesize the [Rh 2 (OAc)(tfa) 3 ] dirhodium complex, the same protocol already described to prepare the [cis-Rh 2 (OAc) 2 (tfa) 2 ] complex was used by slightly modifying the reaction time. 23 In particular, dirhodium tetraacetate [Rh 2 (OAc) 4 ] was treated with an excess of trifluoroacetic acid (TFA), at room temperature, to give, after 6 h, the [Rh 2 (OAc) (tfa) 3 ] compound in a good yield (55%) as a blue powder. 1 H and 19 F NMR data were in agreement with the literature values (see ESI Fig.…”

“…3A in ref. 23). In the spectrum of [Rh 2 (OAc)(tfa) 3 ] collected under these conditions, several peaks were observed and they…”