225780-05-2Relevant academic research and scientific papers
New studies on the reactivity of allyl difluorophosphate palladium complexes: Synthesis of the first difluorophosphate metallocene derivatives
Fernandez-Galan, Rafael,Manzano, Blanca R.,Otero, Antonio
, p. 271 - 282 (2007/10/03)
The reaction of [Pd(η3-2Me-C3H4)(μ-PO2F 2)]3 1, previously synthesized by us, with P- or S-donor ligands leads to the new derivatives [Pd(η3-2Me-C3H4)(PO2F 2)L] (L=PMePh2; P(OR)3, R=Me, Et, Ph; SPPh3) and [Pd(η3-2Me-C3H4)L2]PO 2F2 (L=SPPh3). The neutral and ionic derivatives with L=tetrahydrothiophene, were detected by 1H-NMR. The fluxional behavior of SPPh3 complexes has been analyzed and a dissociation of SPPh3 ligand evidenced. When 1 is made to react with M(η5-C5R5)2Cl2 (M=Ti, R=H, Me; M=Mo, R=H) the new metallocene derivatives M(η5-C5R5)2(PO2F 2)2 are obtained. Using M(PPh3)PF6 (M=Ag, Cu) the complex [Pd(η3-2Me-C3H4)(PPh3) 2]PF6 and M(PO2F2)x (M=Ag, x=1; M=Cu; x=2) are formed. A similar reaction takes place between [Pd(η3-2Me-C3H4)(PO2F 2)(PPh3)] and Ag(ClO4)PPh3. With AuPPh3PF6 and 1 no reaction is observed. The derivatives trans-[PdCl(μ-Cl)(PR3)]2 (R=Ph, Cy) and [Pd(η3-2Me-C3H4)(PhCN)2]PO 2F2 are formed after the reaction of [Pd(η3-2Me-C3H4)(PO2F 2)(PR3)] and PdCl2(PhCN)2. 1 or [Pd(η3-2Me-C3H4)(PO2F 2)(PPh3)], 2, does not react with weak acids However, HCl gives rise to [Pd(η3-2Me-C3H4)Cl(PPh3)] after the reaction with 2. HBF4 also reacts with 1 or 2 and by means of 19F-NMR studies at low temperatures BF4- coordination has been observed when a non-coordinating solvent is used.
