A new synthetic pathway to Chatt-type Mo(0) and W(0) bis(dinitrogen) complexes with the ligand prP4 is presented (prP4 is a linear tetraphos ligand with two ethylene bridges and a central propylene bridge). The synthesis starts from MoCl5 and WCl6, respectively, employing Mg as reductant. Whereas the electrochemical reduction of the oxido–iodido–molybdenum(IV) complex [Mo(O)I(meso-prP4]+ (1) only gave trans-[Mo(N2)2(meso-prP4)] (2a; Römer et al., Eur. J. Inorg. Chem.2008, 3258), the direct synthesis under normal conditions affords both trans and cis complexes 2a and 2b. The reaction products are characterised by vibrational and NMR spectroscopy. Moreover, a single-crystal X-ray structure determination of cis-α-[Mo(N2)2(rac-prP4)] (2b) is performed. In contrast to the trans bis(dinitrogen)molybdenum(0) complex 2a supported by the meso prP4 ligand the corresponding cis-complex is exclusively coordinated by the rac isomer of prP4. The reactivity of 2 with acids is investigated as well, leading to the NNH2 complex [MoF(NNH2)(meso-prP4)]BF4 (15). Analogous results are obtained with the tungsten complexes.
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