Noble‐Gas Difluoride Complexes of MOF4 (M=Mo, W); Syntheses, Structures and Bonding of NgF2 ⋅ MOF4 and XeF2 ⋅ 2MOF4 (Ng=Kr, Xe)

The NgF2 ⋅ MOF4 (Ng=Kr, Xe; M=Mo, W) and XeF2 ⋅ 2MOF4 complexes were synthesized in anhydrous HF (aHF) solvent and melts, respectively. Their single‐crystal X‐ray diffraction (SCXRD) structures show NgF2 ⋅ MOF4 and XeF2 ⋅ 2MOF4 have Ft−Ng−Fb‐ ‐ ‐M arrangements, in which the NgF2 ligands coordinate to MOF4 through Ng−Fb‐ ‐ ‐M bridges. The XeF2 ligands of XeF2 ⋅ 2MOF4 also coordinate to F3OM−Fb’‐ ‐ ‐M'OF4 moieties through Xe−Fb‐ ‐ ‐M bridges to form Ft−Xe−Fb‐ ‐ ‐M(OF3)−Fb’‐ ‐ ‐M'OF4, where XeF2 coordinates trans to the M=O bond and Fb’ coordinates trans to the M’=O bond. The Ng−Ft, Ng−Fb, and M‐ ‐ ‐Fb bond lengths of NgF2 ⋅ nMOF4 are consistent with MOF4 and F3OM−Fb’‐ ‐ ‐M'OF4 fluoride‐ion affinity trends: CrOF4