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High‐valent Molybdenum Imido Complexes with Tethered Olefins
Author(s) -
Siewert Inke,
Limberg Christian,
Ziemer Burkhard
Publication year - 2006
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200500508
Subject(s) - molybdenum , chemistry , olefin fiber , propene , medicinal chemistry , catalysis , crystal structure , olefin metathesis , coordination sphere , stereochemistry , crystallography , organic chemistry , metathesis , polymerization , polymer
Against the background of the (propene)Mo(=O)(=NH) and (allyl)Mo(=O)(=NH) surface species suggested as intermediates of the SOHIO process the potential of H 2 N–C 6 H 4 –CH 2 – CH=CH–CH 3 , ( I ), for the introduction of chelating imido/olefin or imido/allyl ligands at highvalent Mo centres was tested. Reaction of I with Na 2 [MoO 4 ] and trimethylchlorosilane yielded [Cl 2 Mo(=N–C 6 H 4 –CH 2 –CH=CH–CH 3 ) 2 (dme)] ( 1 ), containing pendant olefinic arms. All attempts to introduce the olefin into the coordination sphere of the Mo centre failed. The same observation was made with [Cl 2 Mo(=O)(=N–C 6 H 4 –CH 2 –CH=CH–CH 3 )(dme)] ( 2 ), synthesised via a commutation reaction from 1 and[(dme)Cl 2 Mo(=O) 2 ]. Reaction of three equivalents of I with [CpMoCl 4′ ] yields [CpCl 2 Mo(=N–C 6 H 4 –CH 2 –CH=CH–CH 3 )], ( 3 ), again with a pendant olefin arm; the products of experiments aiming at coordinating it to the Mo atom eluded isolation. I thus does not seem suitable for the synthesis of complexes with imido/olefin or imido/allyl ligands. However, products 1 – 3 , (two of which ( 1 , 3 ) were also characterised by single crystal X‐ray diffraction) are nevertheless interesting, e.g., with respect to the grafting of molybdenum complexes on the surfaces of solid supports to obtain heterogeneous oxidation catalysts.