A standardized and versatile electrochemical batch reactor that has wide applicability in both organic and inorganic synthesis and analytical electrochemistry has been developed. A variety of synthetic electrochemical transformations have been performed to showcase the versatility and demonstrate the reactor, including the synthesis of five Cu(I)-NHC, two Au(I)-NHC and one Fe(II)-NHC complex, as well as an Fe(III)-salen complex. The reactor is based on a commercially available vial with an adapted lid, making it inexpensive and highly flexible. It features a fixed interelectrode distance which is crucial for reproducibility, along with the ability to accommodate a variety of interchangeable electrode materials. The reactor has also been used in conjunction with a parallel plate allowing rapid screening and optimization of an organic electrochemical transformation. Cyclic voltammetry has been performed within the reactor on a range of imidazolium salt analytes with the use of an external potentiostat. The ability to use this reactor for both analytical and synthetic organic and inorganic chemistry is enabled by a flexible and characterizable design.

The reactions of trans-[SnF4(PMe3)2] with one, two or three equivalents of Me3SiO3SCF3 (TMSOTF), respectively, in anhydrous CH2Cl2 form six-coordinate [SnF4-n(PMe3)2(OTf)n] (n = 1-3), which have been characterised by microanalysis, IR...

The reaction of [GeF4L2], L = dmso (Me2SO), dmf (Me2NCHO), py (pyridine), pyNO (pyridine-N-oxide), OPPh3, OPMe3, with Me3SiO3SCF3 (TMSOTf) and monodentate ligands, L, in a 1:1:1 molar ratio in anhydrous CH2Cl2 formed the monocations [GeF3L3][OTf]. These rare trifluoro-germanium (IV) cations were characterised by microanalysis, IR, 1H, 19F{1H} and, where appropriate, 31P{1H} NMR spectroscopy. The 19F{1H} NMR data show that in CH3NO2 solution the complexes exist as a mixture of mer and fac isomers, with the mer isomer invariably having the higher abundance. The X-ray structure of mer-[GeF3(OPPh3)3][OTf] is also reported. The attempts to remove a second fluoride using a further equivalent of TMSOTf and L were mostly unsuccessful, although a mixture of [GeF2(OAsPh3)4][OTf]2 and [GeF3(OAsPh3)3][OTf] was obtained using excess TMSOTf and OAsPh3. The reaction of [GeF4(MeCN)2] with TMSOTf in CH2Cl2 solution, followed by the addition of 2,2′:6′,2”-terpyridine (terpy) formed mer-[GeF3(terpy)][OTf], whilst a similar reaction with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-tacn) in MeCN solution produced fac-[GeF3(Me3-tacn)][OTf]. Dicationic complexes bearing the GeF22+ fragment were isolated using the tetra-aza macrocycles, 1,4,7,10-tetramethyl-1,4,7,10-tetra-azacyclododecane (Me4-cyclen) and 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane (Me4-cyclam), which reacted with [GeF4(MeCN)2] and two equivalents of TMSOTf to cleanly form the dicationic difluoride salts, cis-[GeF2(Me4-cyclen)][OTf]2 and trans-[GeF2(Me4-cyclam)][OTf]2. The 19F{1H} NMR spectroscopy shows that in CH3NO2 solution there are four stereoisomers present for trans-[GeF2(Me4-cyclam)][OTf]2, whereas the smaller ring-size of Me4-cyclen accounts for the formation of only cis-[GeF2(Me4-cyclen)][OTf], and is confirmed crystallographically. New spectroscopic data are also reported for [GeF4(L)2] (L = dmso, dmf and pyNO). Density functional theory calculations were used to probe the effect on the bonding as fluoride ligands were sequentially removed from the germanium centre in the OPMe3 complexes.