Hydroxopalladium(IV) complexes prepared using oxygen or hydrogen peroxide as oxidants.

The cycloneophylpalladium(II) complexes [Pd(CH2CMe2C6H4)(κ2-N,N'-L)], 1 or 2, with L = RO(CH2)3N(CH2-2-C5H4N)2, with R = H or Me, respectively, react with either dioxygen or hydrogen peroxide in the presence of NH4[PF6] to give rare examples of the corresponding hydroxopalladium(IV) complexes [Pd(OH)(CH2CMe2C6H4)(κ3-N,N',N''-L)][PF6], 3 or 4. The complexes 3 and 4 are stable at room temperature and have been structurally characterized. On heating a solution of 3 or 4 in moist dimethylsulphoxide, selective reductive elimination with C(sp2)-O bond formation is observed, followed by hydrolysis, to give the corresponding pincer complex [Pd(OH)(κ3-N,N',N''-L)][PF6] and 2-t-butylphenol as major products. A more complex reaction occurs in chloroform solution. The mechanisms of reaction are discussed, supported by DFT calculations.

A Bridging Peroxide Complex of Platinum(IV).

The photolysis of the allylplatinum(IV) complex [PtBr(C3H5)(4-MeC6H4)2(bipy)], 1, bipy = 2,2'-bipyridine, in air yielded [{PtBr(4-MeC6H4)2(bipy)}2(µ-O2)], 2, the first diplatinum(IV) complex containing a single bridging peroxide ligand. The PtO-OPt bond distance in 2 is 1.481(3) Å. Complex 2 is thought to be formed by homolysis of the allyl-platinum bond of 1, followed by reaction of the platinum(III) intermediate [PtBr(4-MeC6H4)2(bipy)] with oxygen.

Mild and selective Pd-Ar protonolysis and C-H activation promoted by a ligand aryloxide group.

A bidentate nitrogen-donor ligand with an appended phenol group, C5H4NCH[double bond, length as m-dash]N-2-C6H4OH, H(L1) was treated with a palladium cycloneophyl complex [Pd(CH2CMe2C6H4)(COD)], with both Pd-aryl and Pd-alkyl bonds, to give a Pd-alkyl complex, [Pd(CH2CMe2C6H5)(κ3-N,N',O-OC6H4N[double bond, length as m-dash]CH(2-C5H4N))], 1. The cleavage of the Pd-aryl bond and the deprotonation of the ligand phenol to afford a bound aryloxide, indicates facile Pd-aryl bond protonolysis. Deuterium labelling experiments confirmed that the ligand phenol promotes protonolysis and that the reverse, aryl C-H activation, occurs under very mild reaction conditions (within 10 min at room temperature). An unusual isomerization of the Pd-alkyl complex 1 to a Pd-aryl complex, [Pd(C6H4(2-t-Bu))(κ3-N,N',O-OC6H4N[double bond, length as m-dash]CH(2-C5H4N))], 2, was observed to give an equilibrium with [2]/[1] = 9 after 5 days in methanol. The isomerization requires that both aryl C-H activation and Pd-alkyl protonolysis steps occur. The very large KIE value (kH/kD = ca. 40) for isomerization of 1 to 2, suggests a concerted SE2-type mechanism for the Pd-alkyl protonolysis step.

Supramolecular Polymer and Sheet and a Double Cubane Structure in Platinum(IV) Iodide Chemistry: Solution of a Longstanding Puzzle.

The complexes [PtMe2(L)], L = 2-C5H4NCH2NH-x-C6H4OH (x = 2, 3, or 4), react with iodine to form [PtI2Me2(L)], by trans oxidative addition, when x = 3 or 4, and they are shown to have polymeric or sheet structures formed through NH···I hydrogen bonding. However, ligand dissociation occurs when x = 2 to give [(PtI2Me2) n ] and, with methyl group transfer, the complex [(PtIMe3·PtI2Me2)2]. This tetraplatinum cluster complex is shown to have a double cubane structure, thus solving a longstanding puzzle.

Pincer-plus-one ligands in self-assembly with palladium(ii): a molecular square and a molecular tetrahedron.

The combination of a palladium(ii) precursor with a diimine-phenol ligand and an oxidant (H2O2 or O2) under different conditions has, serendipitously, given both a molecular square and a molecular tetrahedron by self-assembly of building blocks comprising palladium(ii) centres coordinated to the oxidised forms of the ligand.