Issue 13, 2011
From the journal:

Dalton Transactions

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(N2)2(meso-prP4)]; M = Mo, W†‡

René Römer,a   Christian Gradert,a   Alexander Bannwarth,a   Gerhard Peters,a   Christian Näthera  and  Felix Tuczek*a  

* Corresponding authors

a Institut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Straße 2, Max Eyth, Germany
E-mail: ftuczek@ac.uni-kiel.de

Abstract

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.

Graphical abstract: 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(N2)2(meso-prP4)]; M = Mo, W

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Article information

DOI
https://doi.org/10.1039/C0DT01646B
Article type
Paper
Submitted
26 Nov 2010
Accepted
12 Jan 2011
First published
23 Feb 2011

Dalton Trans., 2011,40, 3229-3236

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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(N2)2(meso-prP4)]; M = Mo, W

R. Römer, C. Gradert, A. Bannwarth, G. Peters, C. Näther and F. Tuczek, Dalton Trans., 2011, 40, 3229 DOI: 10.1039/C0DT01646B

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