SYNTHESIS, CRYSTAL STRUCTURES AND SOME REACTIONS OF ZEROVALENT TRIS DERIVATIVES OF CHROMIUM, MOLYBDENUM, TUNGSTEN, VANADIUM, NIOBIUM AND TANTALUM

Article abstract of DOI:10.1016/0022-328X(84)80680-4

Co-condensation of the vapours of the metals M = Cr, Mo, W, V, Nb, Ta with an excess of bis-1,2-(dimethylphosphino)ethane (dmpe) gives the neutral, zerovalent compounds M(dmpe)3.X-ray structure analysis shows that the crystals are isomorphous (cubic, space group Im3m, a 10.922(3), 11.058(5), 11.040(5), 11.041(3), 11.194(4) and 11.164(3) Angstroem respectively) and contain isolated molecules which have an essentially octahedral distribution of the six phosphorus atoms about the metal centre.The compound Cr(dmpe)3 reacts with methyl iodide giving trans-CrI2(dmpe)2.Mo(dmpe)3 reacts with hydrochloric acid forming the dihydrido derivative isolated as the hexafluorophosphate salt 2.Mo(dmpe)3 also reacts with iodine or methyl iodide forming the paramagnetic cation ⁺ which was isolated as the hexafluorophosphate salt.