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Stereoselective Synthesis of the First Chatt‐Type Bis(dinitrogen)‐Molybdenum(0) Complex with a Tetraphosphane Ligand
Author(s) -
Römer René,
Stephan Gerald,
Habeck Carsten,
Hoberg Christian,
Peters Gerhard,
Näther Christian,
Tuczek Felix
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800417
Subject(s) - chemistry , molybdenum , denticity , ligand (biochemistry) , stereoselectivity , bridging ligand , medicinal chemistry , catalysis , stereochemistry , nuclear magnetic resonance spectroscopy , molecule , organic chemistry , crystal structure , biochemistry , receptor
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)