Basicity of transiton metal carbonyl complexes : XIII. Reactions of the π-cyclopentadienyl complexes of molybdenum and tungsten with aprotic acids |
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Authors: | A.G. Ginzburg G.G. Aleksandrov Yu.T. Struchkov V.N. Setkina D.N. Kursanov |
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Affiliation: | Institute of Organoelement Compounds, USSR Academy of Sciences, Moscow 117813, Vavilov st. 28 U.S.S.R. |
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Abstract: | The aprotic acids HgCl2 and SnX4 (X Cl, Br) react with the π-complexes C5H5M(CO)(NO)(L) (II, M Mo W; L PPh3) by attack at the metal center. With HgCl2 complexes II yield stable neutral 1:1 adducts CpM(CO)(NO)(L)HgCl2(III). In the case of SnCl4, complexes II initially produce the ionic 1:2 adducts [CpM(CO)(NO)(L)(SnCl3)]+SnCl5-(IV) which, as a result of oxidative elimination of CO, turn into the neutral complexes CpM(NO)(L)(SnCl3)(Cl)(V). In reactions of II with SnBr4 the corresponding CpM(NO)(L)(SnB3)(Br) complexes are formed directly. The formation of III–V is accompanied by a considerable increase of the frequencies ν(CO) and ν(NO). The structures of the complexes IV (M Mo) and V (M Mo) have been established by an X-ray structure analysis. |
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