Präparative, spektroskopische und kristallographische Untersuchungen an Phosphinato-Komplexen des Rheniums mit verschiedenen einzähnigen Liganden

E k k e h a r d L i n d n e r * , S a d e k T r a d , S i g u r d H o e h n e u n d H a n s H e n n i n g O e t j e n Institut für Anorganische Chemie der Universität Tübingen, Auf der Morgenstelle 18, D-7400 Tübingen 1 Z. Naturforsch. 34b, 1203-1212 (1979); eingegangen a m 28. Mai 1979 Phosphinato Complexes, Rhenium(I) , MS, I R , Raman, X R a y The stable phosphinato complexes [^ -R 2 P0 2 Re(C0 )3L ] „ (1, 2b-f) [L = T H F (a), py (b), N H 3 (c), P(C6H5)3 (d), A S ( C 6 H 5 ) 3 (e), P (C 6 Hn) 3 (f), 0 ( C 2 H 5 ) 2 (g)] are obtained b y addition of the ligands L to the compounds 0 R 2 P 0 2 R e ( C 0 ) 3 ] M (1, 2) [R = CH 3 (1), C 6 H 5 (2)] at 20-40 °C (1, 2c: — 3 5 °C). 1, 2b, d, e are also formed when T H F in 1, 2a is substituted b y the ligands b, d, and e. The unstable ether adducts 1, 2 g which result photochemically from Re2(CO)io and the acids R 2 P 0 2 H , are transformed to 1, 2 b y elimination of ether. A t 20 °C 1, 2 a react with liquid ammonia to give the ionic complexes [ (0C)3Re(NH3)3][0 2PR 2 ] (1, 2h). On the basis of their mass and vibrational spectra, and a crystallographic investigation, the methyl [ l a f ] and phenyl compounds [2 a f ] are dimeric and oligomeric, respectively. The rhenium atoms are bridged via R 2 P 0 2 ~ ligands (phosphinato-0 ,0 ' ) . l a crystallizes monoclinic in the space group C2/m with Z = 2.