Treating [Cp*V(l-Cl) 2 ] 3 (Cp* = C 5 Me 5 ) and [(2,6-i-Pr 2 C 6 H 3 N) 2 MoMe 2 ], respectively, with Me 3 SnF afforded the title compounds [Cp*V(l-F) 2 ] 4 (1) and [(2,6-i-Pr 2 C 6 H 3 N) 2 MoF 2 ] ´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 A Ê . A hydrolyzed product of 2, [(2,6-i-Pr 2 C 6 H 3 N) 6 Mo 4 (l 3 -F) 2 Me 2 (l-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 l-O and two l 3 -F atoms. The geometries around the two Mo atoms can be described having distorted trigonal bipyramidal and distorted octahedral coordination spheres, respectively. The Mo±(l-O) bond lengths are 1.813 A Ê (average) for five coordinated Mo atoms and 2.030 A Ê (average) for those of six coordinated, respectively, indicating an additional p bonding between five coordinated Mo atoms and the l-O atoms. The Mo±(l 3 -F) distances range from 2.291 to 2.352 A Ê .