1173278-07-3

Upstream product

• 57322-00-6 1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane 
• 7727-37-9 nitrogen 
• 10241-05-1 molybdenum(V) chloride 

Downstream Products

• 1285542-21-3 [MoF(NNH₂)(meso-1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane)]BF₄ 
• 1285542-22-4 [Mo(NNH₂)(1,1,4,8,11,11-hexaphenyl-1,4,8,11-tetraphosphaundecane)(OTf)]⁽¹⁺⁾ 

Relevant academic research and scientific papers

Stereoselective synthesis of the first chatt-type bis(dinitrogen)- molybdenum(0) complex with a tetraphosphane ligand

The first Chatt-type Mo0 dinitrogen complex with a tetraphosphane ligand has been prepared and characterized by NMR as well as infrared and Raman spectroscopy. Importantly, the employed reaction route allows the stereospecific synthesis of this complex as trans-[Mo(N2) 2(meso-prP4)] (prP4 = a tetraphos ligand with a central propylene bridge). The stereoselectivity in the reaction course is induced by the oxido-iodido-molybdenum(IV) precursor [Mo(O)I(prP 4)]+ which directs both phenyl groups of the bridging P atoms of prP4 into a meso configuration. The paper establishes a general strategy to synthesize mononuclear Mo0 dinitrogen and related molybdenum complexes with multidentate phosphane ligands which has not been possible to date. Moreover, the obtained molybdenum tetraphos N2 complex should exhibit a higher thermodynamic stability in the reactions of the Chatt cycle of synthetic nitrogen fixation than the conventional bis(diphos) complexes, due to the linkage of the two diphosphane units by an alkyl bridge. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

One-step synthesis of Mo(0) and W(0) bis(dinitrogen) complexes with the linear tetraphosphine ligand prP4: Stereoselective formation of cis-[M(N2)2(rac-prP4)] and trans-[M(N 2)2(meso-prP4)]; M = Mo, W

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-prP 4)] (2a; Roemer 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.