The reaction of Na[3,5-di-(tert-butyl)-1,2,4-triphospholyl] (Na-2) with R 3 SnCl (R Ph, Me, nBu) affords the 1-triorganylstannyl-3,5-di(tert-butyl)-1,2,4-triphospholes 4 a ± 4 c in very good yields. A rapid suprafacial [1,5]-sigmatropic shift of the SnPh 3 group in 4 a with DG = 31.5 kJ mol À1 indicates a labile

The replacement of sp2 C−R fragments by isolobal phosphorus atoms may cause a reversal of the order of the frontier orbitals on metallocenes (see scheme). Hexaphosphamanganocene 1 is a good example to demonstrate this effect, as it exhibits the ground state 2A, not previously observed for manganocene derivatives. The spin‐density distribution of 1 mainly resembles a manganese d z 2 orbital. In contrast to decamethylmanganocene, 1 is not Jahn–Teller active!

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Der Ersatz von sp2‐CR‐Fragmenten durch die isolobalen Phosphoratome kann bei Metallocenen zu einer Umkehr der Reihenfolge der Grenzorbitale führen (siehe Schema). Ein Beispiel dafür ist Hexaphosphamanganocen 1, welches den bislang bei Manganocenderivaten noch nicht beobachteten Grundzustand 2A aufweist. Die Spindichteverteilung von 1 entspricht weitgehend einem Mn‐d italicz 2‐Orbital. Deshalb ist 1 im Gegensatz zum Decamethylmanganocen nicht Jahn‐Teller‐aktiv!

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