The chemistry of (fulvalene)dimolybdenum hexacarbonyl: a rigidly held dinuclear transition-metal complex

Oligocyclopentadienyl Transition Metal Complexes

“…9b, 12 On the other hand (and as expected for W), the dihydride 45 turned out to be considerably more stable and therefore subject of further investigation. …”

“…24a This reactivity parallels that of FvMo 2 (CO) 6 Me 2 (Scheme 10), 12 CpMo(CO) 3 Me, 35 and CpW(CO) 3 Me. 35 The source of the fourth H (necessary for CH 4 ) in the W system is a second methyl group, and it differs, in a puzzling way, from that for FvMo 2 (CO) 6 Me 2 and CpMo(CO) 3 Me (the source of the hydrogen being mostly the ring systems) and CpW(CO) 3 Me (solvent).…”

“…Thermolysis (100 ºC) led to efficient generation of propene and 5 by an unprecedent retro-ene reaction on a dinuclear matrix. 12 (OC) 3 6 ] showed it to contain a planar Fv ring system bonded to the two metal centers in trans fashion, 24a as observed in analogous FvM 2 systems lacking M-M bonds 5a,9b,12,17f,h,32,33 (with the exception of those endowed with addition M-M bridges).…”

“…It was based on the discovery that dihydrofulvalene, 1, is relatively stable when pure and can therefore be converted in the presence of metal carbonyls, "M(CO)" at elevated temperatures to a number of fulvalene homodinuclear compounds ( 12 , and Mo(CO) 6 , respectively. Efficient syntheses of complexes 4 and 6 required the readily accessible propionitrile complexes Cr(NCEt) 3 (CO) 3 and W(NCEt) 3 (CO) 3 , respectively.…”

μ-(η5:η5-Fulvalene)-bis[dicarbonyl(trimethylphosphine)molybdenum](Mo–Mo)

“…where Cp is the centroid of a cyclopentadienyl moiety] is the largest known torsion angle of any compound reported containing a metal-metal bond and the fulvalene ligand (Drage & Volhardt, 1986). Other reported fulvalene complexes containing a metal-metal bond have small torsion angles and eclipsed conformations of the non-fulvalene ligands (Drage & Volhardt, 1986;Abrahamson & Heeg, 1984).…”