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.

Models for Cooperative Catalysis: Oxidative Addition Reactions of Dimethylplatinum(II) Complexes with Ligands Having Both NH and OH Functionality.

The role of NH and OH groups in the oxidative addition reactions of the complexes [PtMe2(κ2-N,N'-L)], L = 2-C5H4NCH2NH-x-C6H4OH [3, x = 2, L = L1; 4, x = 3, L = L2; 5, x = 4, L = L3], has been investigated. Complex 3 is the most reactive. It reacts with CH2Cl2 to give a mixture of isomers of [PtMe2(CH2Cl)(κ3-N,N',O-(L1-H)], 6, and decomposes in acetone to give [PtMe3(κ3-N,N',O-(L1-H)], 7, both of which contain the fac tridentate deprotonated ligand. Complex 3 reacts with MeI to give complex 7, whereas 4 and 5 react to give [PtIMe3(κ2-N,N'-L2))], 8, or [PtIMe3(κ2-N,N'-L3)], 9, respectively. Each complex 3, 4, or 5 reacts with either dioxygen or hydrogen peroxide to give the corresponding complex [Pt(OH)2Me2(κ2-N,N'-L)], 10, L = L1; 11, L = L2; 12, L = L3. The ligand L3 in complexes 9 and 12 is easily oxidized to the corresponding imine ligand 2-C5H4NCH=N-4-C6H4OH, L4, in forming the complexes [PtIMe3(κ2-N,N'-L4)], 13, and [Pt(OH)2Me2(κ2-N,N'-L4)], 14, respectively. The NH and OH groups play a significant role in supramolecular polymer or sheet structures of the complexes, formed through intermolecular hydrogen bonding, and these structures indicate how either intramolecular or intermolecular hydrogen bonding may assist some oxidative addition reactions.

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.

Coordination chemistry of mercury(ii) with 2-pyridylnitrones: monomers to polymers.

The coordination chemistry of mercury(ii) halides, HgX2, X = Cl, Br, I, with N-methyl-α-(2-pyridyl)nitrone, L1, and N-t-butyl-α-(2-pyridyl)nitrone, L2, is reported. The structures of 1 : 1 complexes [HgX2L], X = Cl, L = L1; X = Br, L = L2, 2 : 1 complexes [(HgX2)2L], X = Br or I, L = L1; X = Cl or I, L = L2, and a unique compound [(HgBr2)5(L2)3] have been determined. In the 1 : 1 and 1 : 2 complexes, the ligand L1 adopts the anti conformation, and is either monodentate or bridging, while the ligand L2 adopts the syn conformation and acts as a chelate ligand. In the compound [(HgBr2)5(L2)3] the ligand L2 is present in both syn-chelate and anti-bridging bonding modes. Secondary intermolecular bonding, involving OHg or XHg interactions, can lead to association of the molecular compounds to form polymers of several kinds. In solution, the complexes are labile and the crystalline products do not necessarily reflect the reaction stoichiometry.

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.