Sie befinden Sich nicht im Netzwerk der Universität Paderborn. Der Zugriff auf elektronische Ressourcen ist gegebenenfalls nur via VPN oder Shibboleth (DFN-AAI) möglich. mehr Informationen...
Metallabis(dialkylphosphito)‐Einheiten als Komplexbildner, VI. Darstellung und Komplexbildungsvermögen des metallorganischen Chelatliganden {C5Me5RhI[P(O)(OMe)2]2}
Complexes Containing Metallabis(dialky1phosphito) Units, VI1. – Synthesis and Complex‐Forming Properties of the Organometallic Chelating Ligand {C5Me5RhI[P(0)(OMe)2]2}‐
The dinuclear complexes [C5Me5NiBr]2 and [C5Me5RhI2]2 react stepwise with P(OMe)3 by cleavage of the halide bridges and a subsequent Michaelis‐Arbuzov‐type reaction to give the neutral compounds C5Me5Ni[P(O)(OMe)2][P(OMe)3] (3) and C5Me5RhI[P(O)(OMe)2][P(OMe)3 (6). Treatment of 6 with an equimolar amount of NaI gives the sodium salt of the {C5Me5RhI[P(O)(OMe)2]2}− anion Na[L] (7) isolated as an adduct with 0.6 NaI. Reaction 7 with H2SO4 in water leads to the formation of the protonated complex C5Me5RhI[P(O)(OMe)2][P(OH)(OMe)2] (8), from which on treatment with thallium acetylacetonate C5Me5RhI[P(O)(OMe)2]2TI (9) is obtained. The X‐ray structural analysis of 9 reveals that the organometallic anion L− is coordinated as a bidentate ligand by the P = O oxygen atoms to thallium, L− also behaves as a bidentate chelating ligand in the complexes [L]2Mg(OH2)2 (12), [L]2Zn (13) and [L]2UO2 (14), whereas it is presumably coordinated as an O,O′,I‐tripod ligand in the compounds [L]PtMe3 (10) and [L]2Cu (11). In acid solution 8 reacts with NaBPh4 to give the diphenylborane derivative LBPh2 (15).