The photo‐induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η3‐C3H5)V(CO)4[P(C7H7)3] (1), (η5‐C5H5)V(CO)3[P(C7H7)3] (2), (η7‐C7H7)V(CO)2[P(C7H7)3] (3), (η6‐C6H3Me3)Cr(CO)2[P(C7H7)3] (4), and (η5‐C5H5)Mn(CO)2[P(C7H7)3] (7), in which the olefinic phosphane is coordinated as a conventional two‐electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring (2*, 4*, 7*), were included for comparison. Subsequent photo‐elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four‐electron ligand, leading to (η6‐C6H3Me3)Cr(CO)[P(C7H7)2(η2‐C7H7)] (5) and (η5‐C5H5)Mn(CO)[P(C7H7)2(η2‐C7H7)] (8), respectively. The η2‐coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η6‐C6H3Me3)Cr(CO)[P(C7H7)3][P(OMe)3] (6) and (η5‐C5H5)Mn(CO)[P(C7H7)3][P(OMe)3] (9). The 31P and 13C NMR spectra of all complexes are discussed, and X‐ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido‐bridged dimer, {(η5‐C5H5)Mn(CO)[P(C7H7)2]}2(10).

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Durch chemische Transportreaktionen mit HCl oder Cl2 als Tranportmittel (1050 → 900 °C bzw. 850 → 750 °C) konnten die festen Lösungen (ZnxCo1—x)2GeO4, and (MnxZn1—x)2GeO4 präpariert werden. ZnGeO3, das in reiner Form unbekannt ist, kann in Form von Mischkristallen (MnxZn1—x)GeO3 (x > 0, 5) stabilisiert werden.