Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordinationElectronic supplementary information (ESI) available: Full experimental procedures and characterisation data, original IR and NMR spectra for the compounds reported. CCDC 1854218 and 1854219. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8cc05598j

Reaction of WF 6 with AsR 3 (R = Me or Et) in anhydrous CH 2 Cl 2 at low temperature forms the neutral seven-coordinate, [WF 6 (AsR 3 )] (R = Me, Et), the first arsine complexes of WF 6 , whilst o -C 6 H 4 (EMe 2 ) 2 (E = P, As) produces [WF 4 { o -C 6 H 4 (EMe 2 ) 2 } 2 ][WF 7 ] 2 . Crystal structures show the latter contain dodecahedral cations, and present the highest oxidation state metal fluoride complexes known (and the highest possible for tungsten) with soft neutral phosphine and arsine coordination. The dodecahedral [WF 4 { o -C 6 H 4 (EMe 2 ) 2 } 2 ] 2+ dications (E = P, As) present the highest oxidation state metal fluoride complexes with soft donor ligands.