Controlled introduction of functional groups at one P atom in [Cp*Fe(-P)] and release of functionalised phosphines.

By salt metathesis reactions of the anionic complexes of the type [Cp*Fe(-PR)] (R = Bu (1a), Me (1b), -C[triple bond, length as m-dash]CPh (1c); Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with organic electrophiles (XR; X = halogen; R = (CH)Br, (CH)Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [Cp*Fe(-PRR)] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [Cp*Fe(-PRR')] (2a: R = Bu, R' = (CH)Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{Cp*Fe(-PBu)}(CH){Cp*Fe(-PMe)}] (4) and [Cp*Fe(-PRR')] (5) (R = Bu, R' = (CH)PPh) or by abstraction of a phosphine to the asymmetric substituted phosphine Bu(Bn)P(CH)Bn (6).

A convenient route to mixed cationic group 13/14/15 compounds.

The formation of novel cationic mixed main group compounds is reported revealing a chain composed of different elements of group 13, 14, and 15. Reactions of different pnictogenylboranes REBH·NMe (E = P, R = Ph, H; E = As, R = Ph, H) with the NHC-stabilized compound IDipp·GeHBHOTf (1) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene) were carried out, yielding the novel cationic, mixed group 13/14/15 compounds [IDipp·GeHBHERBH·NMe] (2a E = P; R = Ph; 2b E = As; R = Ph; 3a E = P; R = H; 3b E = As; R = H) by the nucleophilic substitution of the triflate (OTf) group. The products were analysed by NMR spectroscopy and mass spectrometry and for 2a and 2b also by X-ray structure analysis.