Stereoselective Synthesis of the First Chatt-Type Bis(dinitrogen)-Molybdenum(0) Complex with a Tetraphosphane Ligand

✍ Scribed by René Römer; Gerald Stephan; Carsten Habeck; Christian Hoberg; Gerhard Peters; Christian Näther; Felix Tuczek

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 308 KB
• Volume: 2008
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200800417

✦ Synopsis

Abstract

The first Chatt‐type Mo^0^ 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(N~2~)~2~(meso‐prP~4~)] (prP~4~ = 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 prP~4~ into a meso configuration. The paper establishes a general strategy to synthesize mononuclear Mo^0^ dinitrogen and related molybdenum complexes with multidentate phosphane ligands which has not been possible to date. Moreover, the obtained molybdenum tetraphos N~2~ 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, 69451 Weinheim, Germany, 2008)