Univerzita Pardubice Fakulta chemicko- technologická

Univerzita Pardubice

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Publikace detail

Propene complexes of molybdenum and tungsten

Autoři: Mrózek Ondřej | Vinklárek Jaromír | Honzíček Jan | Císařová Ivana

Rok: 2019

Druh publikace: ostatní - přednáška nebo poster

Strana od-do: nestránkováno

Tituly:

Jazyk	Název	Abstrakt	Klíčová slova
eng	Propene complexes of molybdenum and tungsten	The allyl cleavage reaction[1] from the fragment [(3 allyl)(5 Cp')Mo] represents important chemical transformation providing numerous of new organometallic complexes such as large family of biologically active compounds of type [(5 Cp')Mo(CO)2(N,NL)][BF4] or mixed complex [(5 Cp)(3 Ind)Mo(CO)2] which has been successfully used for reveal of nature of the indenyl effect.[2,3] Within the allyl cleavage reactions, the 2 propen complexes are often proposed as intermediates nevertheless due to thermal lability, these species are not usually isolated. In fact, even the simple propene complex with unsubstituted Cp ligand was not isolated in solid state due to “facile decomposition to an insoluble black residue”.[1] Herein, we show that N  M intramolecular interaction from rigid quinolyl substituted indenyl stabilizes 2 propene complexes of molybdenum and tungsten. Furthermore, preliminary reactivity of the new propene species will be discussed as well.The propene complexes 1 and 2 were synthesized by the reaction of starting mixed allyl/indenyl compounds [(η3-C3H5){η5-1-(C9H6N)C9H6}M(CO)2] with HBF4 at 30 ºC in CH2Cl2. Although the 1 liberates propene above 20 ºC the 2 is in solid state stable at room temperature. Importantly, the 2 was fully structurally characterized including X ray diffraction. The propene ligand of 1 and 2 might be exchange by various monodentate ligands such as Me2S. On the other hand, acetonitrile induces haptotropic 5  3 rearrangement (Scheme 1) to afford compounds 5 and 6. All described complexes were characterized by means of multinuclear NMR spectroscopy, infrared spectroscopy etc. Moreover, the individual proposed structural types were confirmed by X-ray diffraction. The stabilization of low-hapticity indenyl ligand in case of 5 and 6 will be discussed in terms of quantum-chemical calculations.	molybdenum; tungsten; propene