Several new SeF2(CN)(2)-donor complexes with N or O based donor molecules are reported. Due to orbital overlap effects 12-crown-4 (1,4,7,10-tetraoxacyclododecane) shows unsymmetric ether oxygen coordination. Solvent coordination (secondary bonding interactions, SBI) in SeFx(CN)(4-x) compounds is weak and does not influence decomposition pathways (neutral and anionic). Barriers for decomposition are relatively high in SeF2(CN)(2) but decrease significantly in compounds with higher cyanide content. In the presence of fluoride ions, facile substitution pathways exist; however, reductive elimination is also favored. In the absence of fluoride ions decomposition barriers are higher, but so are substitution barriers (s-metathesis). Therefore, successful isolation of Se(CN)(4) appears to be significantly hampered. In addition, previously unknown trifluoromethyliminoseleniumdifluoride was cleanly synthesized utilizing the instability of SeF(CN)(3) toward reductive FCN elimination (preferred over the thermodynamically favored NCCN elimination) and subsequent FCN incorporation to SeF4 through double F-migration.