Stepwise Conversion of a Platinum Dimethyl Complex to a Perfluorometallacyclobutane Derivative

Abstract

In this report, we have demonstrated proof-in-principle that simple dimethyl metal complexes could be used to generate perfluorometallacyclobutane derivatives. With the new methodology, we have more than doubled the number of known perfluorometallacyclobutanes in the literature. We have also structurally characterized three platinum perfluorometallacyclobutanes and have described a unique transformation whereby one [Pt­(C3F6)] functionality is converted to [Pt­(C3F4O2)]. The new methodology to prepare perfluorometallacyclobutanes also avoids the use of tetrafluoroethylene, which is becoming increasingly difficult to purchase due to the explosion hazards associated with its use.

Metal Centers as Nucleophiles: Oxymoron of Halogen Bond‐Involving Crystal Engineering

“…The I•••Pt distance is longer than that observed in UKEKIG [81] (Figure 10b), and the directionality is slightly worse, indirectly indicating a weaker interaction. The MEP surface of monomeric JUPZEB [86] (Figure 11b) corroborates this fact, since the MEP value over the Pt atom is quite small, which is likely due to the effect of the H atoms of the cyclooctadiene ligand [71] (a) and UKEKIG [81] [86] (b) MEP surface of the (COD)-(perfluoro-3-iodopropyl)-methyl-platinum(II) complex using 0.001 a.u. The MEP values at selected points of the surface are indicated.…”

“…Figure 11. (a) Partial view of the XRD structure of CSD refcode JUPZEB [86]. (b) MEP surface of the (COD)-(perfluoro-3-iodopropyl)-methyl-platinum(II) complex using 0.001 a.u.…”

Fluoroalkylation of a Methylplatinum(II) Complex under Photoirradiation

“…A small amount of [PtMe 3 I] 4 was also obtained, which was ascribed to the liberation of MeI from the initial Pt­(IV) product and its oxidative addition to PtMe 2 (cod). A similar reaction yields the methyl­(fluoroalkyl)­platinum­(II) complexes PtMeR F (L) (L = cod, nbd (norbornadiene), tmeda ( N , N , N ′, N ′-tetramethylethylenediamine); R F = CF 3 , n -C 3 F 7 , i -C 3 F 7 , n -C 4 F 9 ) and/or bis­(fluoroalkyl)platinum complexes . The complexes have been employed as precursors of new fluoroalkyl platinum complexes having various auxiliary ligands .…”

Gold Complexes with Difunctional Perfluoroalkyl Chains: Quantifying the Energy of Aurophilic Interactions in Flexible Open‐Chain Complexes

“…Their unusual reactivity illustrates the potential of C 2 F 4 in the synthesis of valuable fluoroorganic compounds . Only a few perfluorometallacycles with n ≠4 have been reported . Remarkably, fluorinated metallacyclobutanes ( H ) have been proposed as intermediates in metathesis reactions of fluoroolefins …”

“…[37,39,40] Only a few perfluorometallacycles with n ¼ 6 4 have been reported. [45][46][47] Remarkably, fluorinated metallacyclobutanes (H) have been proposed as intermediates in metathesis reactions of fluoroolefins. [48][49][50] Herein we report the first gold complexes containing bridging or chelating (CF 2 ) n chains.…”