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DOI: 10.1039/A704203E (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 4271-4276

Synthesis and reactivity of [Pd2L2R2(µ-OH)2]-type complexes (L = PEt3 or PPh3; R = Me, PhCH2 or Ph). Crystal structure of [Pd2(PPh3)2Ph2(µ-OH)(µ-NHC6H4OMe-p)]

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José Ruiz, Venancio Rodríguez, Gregorio López, Penny A. Chaloner and P. B. Hitchcock

Abstract

The metathesis of Cl– by OH– in [Pd2(PEt3)2R2(µ-Cl)2] gave the binuclear hydroxo complexes [Pd2(PEt3)2R2(µ-OH)2] (R = Me or PhCH2) which in CDCl3 solution exist as 1∶1 mixtures of syn and anti isomers. They reacted with 3,5-dimethylpyrazole (Hdmpz) in 1∶2 molar ratio to yield the corresponding azolate complexes anti-[Pd2(PEt3)2R2(µ-dmpz)2] and with oxalic acid (H2ox), in 1∶1 molar ratio, to afford the corresponding oxalate complexes anti-[Pd2(PEt3)2R2(µ-ox)]. The cleavage of the OH bridges of the di-µ-hydroxo complexes yields the mononuclear [Pd(PEt3)2R(OH)] which in solution are present as 1∶1 mixtures of cis and trans isomers. Binuclear µ-hydroxo-µ-amido palladium complexes [Pd2L2R2(µ-OH)(µ-NHR″)2] (R = Me, L = PEt3; R = Ph, L = PPh3; R″ = Ph, C6H4Me-p, C6H4OMe-p, C6H4Cl-p or C6H4NO2-p) have been prepared by reaction of [Pd2L2R2(µ-OH)2] with the corresponding aromatic amine R″NH2. The NMR data indicate that the isolated complexes are the anti isomers. The crystal structure of complex [Pd2(PPh3)2Ph2(µ-OH)(µ-NHC6H4OMe-p)] has been established; the Pd2ON ring is severely bent.

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