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Reduction of MentPBr 2 M(CO) 5  1 (M = Cr, W) with magnesium in THF yields the diphos­phene complex (CO) 5 M(Ment)P=P(Ment)M(CO) 5  2 as the main product. In addition, a phosphinidene complex, (CO) 5 M(Ment)PM(CO) 5  (3) is also formed. The latter is obtained in larger amounts, if the reaction is carried out in the presence of M(CO) 5 THF. The proposed structures are confirmed by NMR and UV data as well as - in the case of the chromium compounds (2a, 3a) - by crystal structure analysis. Compound 2a is obtained only as the frans-isomer. The P-P distance in 2a (204.0 pm) indicates a double bond which does not participate in the complex formation. The P-Cr distance in 3a (average: 230.3 pm) is within the low est range found for this element combination. Reaction of 2a with LiAlH 4  yields the diphosphane complex (CO) 5 CrMent(H)P-P(H)MentCr(CO) 5  4 as a mixture of “meso” and “rac” diastereomers.

zeitschrift für naturforschung b

Reaktionen koordinierter Liganden, III [1]. Stabilisierung von Dimenthyldiphosphen und Menthylphosphiniden als Brückenliganden in Metallcarbonylkomplexen / Reaction of Coordinated Ligands, III [1]. Stabilization of Dim enthyldiphosphene and Menthylphosphinidene as Bridging Ligands in Metal Carbonyl Complexes