Neutral and cationic germanium(iv) fluoride complexes with phosphine coordination – synthesis, spectroscopy and structures

Abstract

The neutral complexes trans-[GeF₄(PⁱPr₃)₂] and [GeF₄(κ²-L)] (L = CH₃C(CH₂PPh₂)₃ or P(CH₂CH₂PPh₂)₃) are obtained from [GeF₄(MeCN)₂] and the ligand in CH₂Cl₂. Treatment of [GeF₄(PMe₃)₂] with n equivalents of TMSOTf (Me₃SiO₃SCF₃) leads to formation of the series [GeF_4−n(PMe₃)₂(OTf)_n] (n = 1, 2, 3), each of which contains six-coordinate Ge(IV) with trans PMe₃ ligands and X-ray structural data confirm that the OTf groups interact with Ge(IV) to varying degrees. Unexpectedly, [GeF₃(PMe₃)₂(OTf)] undergoes reductive defluorination in solution, forming the Ge(II) complex, [Ge(PMe₃)₃][OTf]₂ (and [FPMe₃]⁺). The bulkier PⁱPr₃ leads to formation of the ionic [GeF₃(ⁱPr₃P)₂][OTf], containing a [GeF₃(ⁱPr₃P)₂]⁺ cation. [GeF₄{o-C₆H₄(PMe₂)₂}], containing the cis-chelating diphosphine, also reacts with n equivalents of TMSOTf to generate [GeF_4−n{o-C₆H₄(PMe₂)₂}(OTf)_n] (n = 1, 2, 3). As for the PMe₃ system, the trifluoride, [GeF₃{o-C₆H₄(PMe₂)₂}(OTf)], is unstable to reductive defluorination in solution, producing the pyramidal Ge(II) complex [Ge{(o-C₆H₄(PMe₂)₂}(OTf)][OTf], whose crystal structure has been determined. The [GeF₃{Ph₂P(CH₂)₂PPh₂}(OTf)] and [GeF₂{Ph₂P(CH₂)₂PPh₂}(OTf)₂], obtained similarly from the parent tetrafluoride complex, are poorly soluble, however their structures were confirmed crystallographically. The complexes in this work have been characterised via variable temperature ¹H, ¹⁹F{¹H} and ³¹P{¹H} NMR studies in solution, IR spectroscopy and microanalysis and through single crystal X-ray analysis of representative examples across each series. Trends in the NMR and structural parameters are also discussed.