Lewis Acid Behavior of MoF<sub>5</sub> and MoOF<sub>4</sub>: Syntheses\nand Characterization of MoF<sub>5</sub>(NCCH<sub>3</sub>), MoF<sub>5</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub><i>n</i></sub>, and MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub><i>n</i></sub> (<i>n</i> = 1, 2)
Janelle Bykowski (11524906)Douglas Turnbull (271094)Nolan Hahn (11524909)René T. Boeré (1850509)Stacey D. Wetmore (696456)Michael Gerken (2078125)
Abstract
The Lewis acid–base adducts\nMoF<sub>5</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub><i>n</i></sub> and MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub><i>n</i></sub> (<i>n</i> = 1, 2) were synthesized from\nthe reactions of MoF<sub>5</sub> and\nMoOF<sub>4</sub> with C<sub>5</sub>H<sub>5</sub>N and structurally\ncharacterized by X-ray crystallography. Whereas the crystal structures\nof MoF<sub>5</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> and MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> are isomorphous containing pentagonal-bipyramidal molecules,\nthe fluorido-bridged, heptacoordinate [MoF<sub>5</sub>(NC<sub>5</sub>H<sub>5</sub>)]<sub>2</sub> dimer differs starkly from\nmonomeric, hexacoordinate MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>). For the weaker Lewis base CH<sub>3</sub>CN, only the 1:1\nadduct, MoF<sub>5</sub>(NCCH<sub>3</sub>), could be isolated.\nAll adducts were characterized by Raman spectroscopy in conjunction\nwith vibrational frequency calculations. Multinuclear NMR spectroscopy\nrevealed an unprecedented isomerism of MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> in solution, with the pyridyl ligands\noccupying adjacent or nonadjacent positions in the equatorial plane\nof the pentagonal bipyramid. Paramagnetic MoF<sub>5</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> was characterized by electron paramagnetic\nresonance (EPR) spectroscopy as a dispersion in solid adamantane as\nwell as in a diamagnetic host lattice of MoOF<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub>; EPR parameters were computed using ZORA\nwith the BPW91 functional using relativistic all-electron wave functions\nfor Mo and simulated using <i>EasySpin</i>. Density functional\ntheory calculations (B3LYP) and natural bond orbital analyses were\nconducted to elucidate the distinctive bonding and structural properties\nof all adducts reported herein and explore fundamental differences\nobserved in the Lewis acid behavior of MoF<sub>5</sub> and MoOF<sub>4</sub>.
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