Reaktionen des diphosphen-komplexes (CO)5CrPhPPPhCr(CO)5
1985; Elsevier BV; Volume: 282; Issue: 1 Linguagem: Inglês
10.1016/0022-328x(85)87141-2
ISSN1872-8561
AutoresJutta Borm, Gottfried Hüttner, Olli Orama, László Zsolnai,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoThe diphosphene compound [(CO)5Cr]2PhPPPh (II), which is formed from [(CO)5Cr]3PhPPPh (I) at 70°C, reacts with HX (X = OH, OMe, NHBu, Cl) to give the diphosphane species [(CO)5Cr]2PhP(H)-(X)PPh (III) with complete threoselectivity. Addition of Br2 to II leads to a mixture of both diastereoisomeric forms of [(CO)5Cr]2PhP(Br)(Br)PPh (IV). Sulfur adds in an erythro-selective 2+1- cycloaddition, yielding the thiadiphosphirane compound Va. Similarly, CH2N2 gives the diphosphirane complex Vb. 2 + 4-Cycloadditions of cyclopentadiene or 2,3-dimethylbutadiene lead to the expected Diels-Alder type addition products VI. The novel compounds have been characterized by analytical and spectroscopic data as well as five X-ray structural analyses. Der Diphosphen-Komplex [(CO5Cr]2PhPPPh (II), der aus [(CO)5Cr]3 PhPPPh (I), bei 70°C erhalten wird, reagiert mit Verbindungen HX (X = OH, OMe, NHBu, Cl) in strenger threo-Selektivität zu den Diphosphan-Komplexen [(CO)5Cr]2PhP(H)(X)PPh (III). II addiert Br2 unter Bildung eines Gemisches der beiden diastereomeren Formen von [(CO)5Cr]2PhP(Br)(Br)PPh (IV). Schwefel wird in einer 2 + 1-Cycloaddition erythroselektiv unter Bildung des Thiadiphosphiran-Komplexes Va addiert. Analog bildet CH2N2 den Diphosphiran- Komplex Vb. 2 + 4-Cycloadditionen mit Cyclopentadien bzw. 2,3-Dimethylbutadien führen zu den erwarteten Diels-Alder-Addukten VI. Die neuen Verbindungen werden analytisch, spektroskopisch sowie in fünf Fällen durch Röntgenstrukturanalysen charakterisiert.
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