Abstract
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 Im3 m, a 10.922(3), 11.058(5), 11.040(5), 11.041(3), 11.194(4) and 11.164(3) Å 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-CrI 2(dmpe) 2. Mo(dmpe) 3 reacts with hydrochloric acid forming the dihydrido derivative isolated as the hexafluorophosphate salt [Mo(dmpe) 3H 2][PF 6] 2. Mo(dmpe) 3 also reacts with iodine or methyl iodide forming the paramagnetic cation [Mo(dmpe) 3] + which was isolated as the hexafluorophosphate salt.
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