Scheme 2. Impact of the solvent on the formation of the undesired (side-)products [W(CO)6I]+ (d(W–C) = 209.3(7) pm, d(C–O) = 112.5(8) pm, d(W–I) = 276.7(1) pm), [W(CO)6(ORF)]+ (d(W–C) = 210.3(3) pm, d(C–O) = 113.5(3) pm, d(W–O) = 201.4(2) pm) and [W(CO)4(ORF)2]+ (d(W–C) = 214.5(3) pm, d(C–O) = 111.4(3) pm, d(W–O) = 189.6(2) pm; av.) as well as their molecular structures (anions are omitted for clarity); all complexes marked with [*] were identified by single-crystal XRD (scXRD); thermal ellipsoids were drawn at 50% probability level; note that the “+…” stands for additional (unidentified) side-products; AgI was formed in all reactions, which turned to a grey precipitate after some time.
