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Die Komplexe C5H5M(2-R′C3H4) (MPd mit R′Me, t-Bu; MPt mit R′Me) reagieren mit einer aquimolaren Menge PR3 (PR3P(i-Pr)3, P(i-Bu)3, PPh2(t-Bu), PCy3, PPhCy2) zu den Verbindungen C5H5M(2-R′C3H4)PR3. Die 1H- und 13C-NMR-Spektren weisen daraufhin, das in den Komplexen C(5H5Pd(2-t-BuC3H4)PR3 und C5H5Pt(2-MeC3H4)PR3 im Temperaturbereich von −60 bis +60°C der Cyclopentadienylligand monohapto- (σ-) und der Allylligand trihapto- (π-) gebunden ist. Die Komplexe C5H5Pd(2-MeC3H4)PR3 liegen in Losung als Isomerengemisch von (h5−C5H5)Pd(h1-allyl)PR3 (A) und (h1−C5H5)Pd(h3-ally)PR3 (B) vor. Fur 14 (PR3PPhCy2) werden die thermodynamischen und kinetischen Daten der intramolekularen Isomerisierung A ⇌ B ermittelt. Die Rontgenstrukturanalyse zeigt, das in 5 auch im Kristall der C5H5-monohapto- und der 2-t-BuC3H4-Ligand trihapto-koordiniert sind. Structurally Dynamical Organometal Complexes, II. Synthesis, Structure, and Dynamics of the Complexes C5H5M(2-R′C3H4)PR3 (MPd, Pt) The complexes C5H5M(2-R′C3H4)(MPd with R′Me, t-Bu; MPt with R′Me) react with an equimolar amount of PR3 (PR3P(i-Pr)3, P(i-Bu)3, PPh2 (t-Bu), PCy3, PPhCy2) to form the compounds C5H5M(2-R′C3H4)PR3. The 1H and 13C NMR spectra indicate that in the complexes C5H5Pd(2-t-BuC3H4)PR3 and C5H5Pt(2-MeC3H4)PR3 within the temperature range of − 60 to +60°C the cyclopentadienyl ligand is monohapto-(σ-)and the allylic ligand trihapto-(π-)bonded. The complexes C5H5Pd(2-MeC3H4)PR3 exist in solution as a mixture of two isomers, (h5−C5H5)Pd(h1-allyl)PR3 (A) and (h1−C5H5)Pd(h3-allyl)PR3 (B). For complex 14 (PR3PPhCy2) the thermodynamic and kinetic data of the intramolecular isomerisation process A ⇌ B have been determined. The X-ray structural analysis of 5 proves that the monohapto coordination of the C5H5 and the trihapto coordination of the 2-t-BuC3H4 ligand is retained in the crystal. |
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