Noble‐Gas Difluoride Complexes of MOF4(M=Mo, W); Syntheses, Structures and Bonding of NgF2 ⋅ MOF4and XeF2 ⋅ 2MOF4(Ng=Kr, Xe)
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AbstractThe NgF2 ⋅ MOF4(Ng=Kr, Xe; M=Mo, W) and XeF2 ⋅ 2MOF4complexes were synthesized in anhydrous HF (aHF) solvent and melts, respectively. Their single‐crystal X‐ray diffraction (SCXRD) structures show NgF2 ⋅ MOF4and XeF2 ⋅ 2MOF4have Ft−Ng−Fb‐ ‐ ‐M arrangements, in which the NgF2ligands coordinate to MOF4through Ng−Fb‐ ‐ ‐M bridges. The XeF2ligands of XeF2 ⋅ 2MOF4also coordinate to F3OM−Fb’‐ ‐ ‐M'OF4moieties through Xe−Fb‐ ‐ ‐M bridges to form Ft−Xe−Fb‐ ‐ ‐M(OF3)−Fb’‐ ‐ ‐M'OF4, where XeF2coordinates trans to the M=O bond and Fb’ coordinates trans to the M’=O bond. The Ng−Ft, Ng−Fb, and M‐ ‐ ‐Fbbond lengths of NgF2 ⋅ nMOF4are consistent with MOF4and F3OM−Fb’‐ ‐ ‐M'OF4fluoride‐ion affinity trends: CrOF4<MoOF4<WOF4≈F3OMo−Fb’‐ ‐ ‐Mo'OF4<F3OW−Fb’‐ ‐ ‐W'OF4. The [‐ ‐(F4OMo)(μ3‐F)H‐ ‐ ‐(μ‐F)H‐ ‐]∞solvate was also synthesized in aHF and characterized by SCXRD. Quantum‐chemical calculations show the M‐ ‐ ‐Fbbonds of NgF2 ⋅ MOF4and XeF2 ⋅ 2MOF4are predominantly electrostatic, σ‐hole type bonds.
