81111-61-7Relevant articles and documents
Reactions of Palladium(II) Allyl Dimers with Palladium(II) Complexes containing ?-Bonded 1,2-Bis(imino)alkyl Groups. Crystal and Molecular Structure of the Zwitterionic Binuclear Compound (Pd(η3-2-MeC3H4)-(R1N=C(PdCl2L)-CMe=NR2)) (L = PPh3, R1 = R2 = C6H4OMe-p)
Crociani, Bruno,Bertani, Roberta,Boschi, Tristano,Bandoli, Giuliano
, p. 1715 - 1728 (1982)
The 1,2-bis(imino)alkylpalladium deerivatives (A), R1N=CL'-CR3=NR2 (R1 = R2 = C6H4OMe-p, R3 = Me, L'= trans-PdClL2 (L = para-substituted triarylphosphine or AsPh3); R1 = R2 = C6H4OMe-p, R3 = H or Ph, L' = trans-PdCl(PPh3); R1 = C6H4OMe-p, R2 = R3 = Me, L' = trans-PdCl(PPh3)2) react with ((PdCl(η3-2-R4C3H4))2) (R4 = H or Me) in the presence of NaClO4 to yield the cationic binuclear complexes (B), (Pd(η3-2-R4C3H4)(R1N=CL'-CR3=NR2))(ClO4), where the 1,2-bis(imino)alkyl group acts as ??'-NN' chelating ligand.In the absence of NaClO4, the reaction leads initially to the formation of the ionic compounds (C), (Pd(η3-2-R4C3H4)(R1N=CL'-CR3=NR2)(PdCl2(η3-2-R4C3H4)), which in a subsecvent slower stage reacts further with exchange of ancillary ligands between the cationic and anionic species, to give the zwitterionic binuclear complexes (D), (Pd(η3-2-R4C3H4)(R1N=CL''-CR3=NR2)) (L'' = cis-PdCl2L), and (PdCl(η3-2-R4C3H4)L).A complex of type (C) (R1 = R2 = C6H4OMe-p, R3 = R4 = Me, L' = PdCl(dppe), dppe = 1,2-bis(diphenylphosphino)ethane) can be isolated from the reaction of the corresponding derivative (A) with ((PdCl(η3-2-MeC3H4))2).The rates of ligand exchange depend markedly on the substituents R1, R2, and R3, on the nature of L, and on solvent.Based on these effects and on 1H n.m.r. spectral data, a mechanism is proposed, which essentially involves opening the five-membered 1,2-bis(imino) ring of the cation promoted by interaction with the anionic species in the intermediate (C).The 1H n.m.r. spectra of (D) indicate the presence of diastereomers which interconvert more or less rapidly at room temperature depending on the substituents R2 or R3 and on the ligand L. the crystal and molecular structure of a typical complex (D) R1 = R2 =C6H4OMe-p, R3 =R4 = Me, L =PPh3) has been determined by X-ray diffraction analysis.Crystals are Orthorombic, a = 20.224(5), b = 20.073(8), c = 19.829(9) Angstroem, space group Pbca, and Z = 8.The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R = 0.086 for 1795 diffractometer data (Mo-Kα radiation).The structural data show that the η3-allyl group is almost symmetrically bound to palladium and its plane forms a dihedral angle of 107.4 deg with the planar five-membered ring.The 1,2-bis(imino)propyl group is ??'-NN' chelated to the Pd(η3-2-MeC3H4)unit and the mean plane of the cycle makes a dihedral angle of 81.9 deg with the co-ordination mean plane of the cis-PdCl(PPh3) group.The major features of the structure are presented by a short Pd-C(imino) bond (1.92(3) Angstroem), indicating a relevant ? contribution, and by a close approach of the R3 substituent to the metal centre of the cis-PdCl2(PPh3) unit (Pd***C(methyl) 3.19 Angstroem).
Mechanism of Migration of Ancillary Ligands in Binuclear Palladium(II) Allyl Complexes
Crociani, Bruno,Uguagliati, Paolo,Belluco, Umberto,Nicolini, Marino
, p. 2303 - 2308 (2007/10/02)
The kinetics and mechanism of the reaction between the binuclear cationic complexes 1)CR3=NR2>Pd(η3-CH2CR4CH2)>ClO4 1 = R2 = C6H4OMe-p, R3 = H, Me, or Ph, R4 = H or Me, L = P(C6H4X-p)3, X = Cl, H, or OMe; R1 = C6H4OMe-p, R2 = R3 = R4 = Me, L =PPh3 or PMePh2> and the anionic allyl derivatives 3-2-R4C3H4)>, (A), leading to the binuclear zwitterionic compounds 1)CR3=NR2>Pd(η3-CH2CR4CH2)>, (2), together with the neutral palladium-allyl products 3-2-R4C3H4)L>, (B), have been studied in 1,2-dichloroethane.This reaction, wich involves exchange of the ancillary ligands L and Cl(1-) between the reactants (1) and (A), proceeds via two parallel steps with rate constants k1 and k2.The faster step consists of a rapid pre-equilibrum association (K) to give the intermediate (1...A), which then rearranges slowly (k2) via opening of the five-membered α-di-imino-cycle in a proposed three-metal transition state.The parallel slower step is formulated as a rate-determing (k1) intramolecular rearrengement of (1) to a labile intermediate (1*), which reacts rapidly with (A) to yield the final products.For this step, the activation process is proposed to involve unassisted α-di-imino ring opening and dissociative exchange of L.The mechanism proposed is based on the activation parameters and on rate effects exerted by the α-di-imino-substituents R2, R3, by the allyl group substituent R4, and by the electronic properties of L.In general, the rate constant k1, k2 and the pre-equilibrum constant K decrease with increasing electron-releasing abilities of the C- and N-imino-substituents; k2 is also depressed by increasing steric demands of the R3 and R4 groups.An increase in the electron-donor properties of L will also bring about a decrease in the overall reaction rate.The effects are generally related to the ease of opening and rearrangement of the ?,?-N,N-chelated α-di-imine in (1) together with the lability of the Pd-L bond.
