Synthesis and Structure of the Tetrameric [Cp*V(μ‐F)2]4 (Cp* = C5Me5); Preparation of the Imido Molybdenum Fluoride [(2,6‐i‐Pr2C6H3N)2MoF2] · THF and the Structural Investigation of [(2,6‐i‐Pr2C6H3N)6Mo4(μ3‐F)2Me2(μ‐O)4]

Treating Cp*V(μ‐Cl)₂]₃ (Cp* = C₅Me₅) and (2,6‐i‐Pr₂C₆H₃N)₂MoMe₂], respectively, with Me₃SnF afforded the title compounds Cp*V(μ‐F)₂]₄ ( 1 ) and (2,6‐i‐Pr₂C₆H₃N)₂MoF₂] · THF ( 2 ). 1 has a tetrameric structure, in which four V atoms can be regarded as being arranged at the vertices of a distorted tetrahedron, with four long edges bridged by one F atom and each of the other two short edges bridged by two F atoms with a mean V–F bond length of 2.00 Å. A hydrolyzed product of 2 , (2,6‐i‐Pr₂C₆H₃N)₆Mo₄(μ₃‐F)₂Me₂(μ‐O)₄] ( 3 ) was characterized by elemental analyses and X‐ray single crystal study. The X‐ray diffraction analysis reveals that 3 has a unique tetranuclear structure, containing two five and two six coordinated Mo atoms connecting each other by four μ‐O and two μ₃‐F atoms. The geometries around the two Mo atoms can be described having distorted trigonal bipyramidal and distorted octahedral coordination spheres, respectively. The Mo–(μ‐O) bond lengths are 1.813 Å (average) for five coordinated Mo atoms and 2.030 Å (average) for those of six coordinated, respectively, indicating an additional π bonding between five coordinated Mo atoms and the μ‐O atoms. The Mo–(μ₃‐F) distances range from 2.291 to 2.352 Å.