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.

Self-assembly of the smallest and tightest molecular trefoil knot.

Molecular knots, whose synthesis presents many challenges, can play important roles in protein structure and function as well as in useful molecular materials, whose properties depend on the size of the knotted structure. Here we report the synthesis by self-assembly of molecular trefoil metallaknot with formula [Au6{1,2-C6H4(OCH2CC)2}3{Ph2P(CH2)4PPh2}3], Au6, from three units of each of the components 1,2-C6H4(OCH2CCAu)2 and Ph2P(CH2)4PPh2. Structure determination by X-ray diffraction revealed that the chiral trefoil knot contains only 54 atoms in the backbone, so that Au6 is the smallest and tightest molecular trefoil knot known to date.

Chemistry of Gold(III) with a Pyridine-Oxaziridine Ligand: Competition between C-O and N-O bond Activation.

The oxaziridine derivative 2-t-butyl-3-(2-pyridinyl)oxaziridine reacted with Na[AuCl4 ].2H2 O to give, after recrystallization from a solvent mixture containing methanol, a mixture of gold(III) complexes which were characterized crystallographically as the amide complex [AuCl2 {κ2 -N,N'-2-C5 H4 NC(=O)N(t-Bu)] and the aldolate complex [AuCl2 {κ2 -N,O-2-C5 H4 NCH(OMe)O)]. It is suggested that these products arise after initial O-N or C-N bond cleavage respectively of the strained oxaziridine ring, after coordination to the gold(III) center. Monitoring of reactions by NMR spectroscopy showed that O-N bond cleavage of the oxaziridine ring was favoured in the presence of a protic solvent.

Supramolecular organometallic chemistry: the platinum(IV) paradigm.

Supramolecular chemistry and the chemistry of alkyl derivatives of the transition metals are both topics of considerable current interest, but the combination of the two fields is still underdeveloped. The challenges are, in large part, experimental in nature. For example, the self-assembly of molecules in supramolecular chemistry often relies on intermolecular hydrogen bonding, but most alkyl-transition metal bonds are cleaved by the protic groups used in hydrogen bond formation. Alkyl-platinum(IV) bonds are inert to protonolysis or attack by other electrophiles under mild conditions, and this has allowed an extensive supramolecular chemistry of organoplatinum(IV) complexes to be developed, as outlined in this perspective review. Highlights include a zeolitic structure, a polyrotaxane, a double helix, a nanotube structure and an example of spontaneous resolution to form a chiral sheet structure.

DFT studies of two-electron oxidation, photochemistry, and radical transfer between metal centres in the formation of platinum(IV) and palladium(IV) selenolates from diphenyldiselenide and metal(II) reactants.

The oxidant diphenyldiselenide reacts with MIIMe2(bipy) (bipy = 2,2'-bipyridine) to form a pre-equilibrium involving weak adducts, from which [MMe2(bipy)]2·Ph2Se2 undergoes rate-limiting dissociation of phenylselenide preceded by the oxidative addition step to obtain [Me2(bipy)M-MMe2(bipy)(SePh)]+. Coordination of PhSe- gives the neutral MIII-MIII bonded dimers [MMe2(bipy)(SePh)]2. The dimers fragment in the presence of light to give radicals [MIIIMe2(bipy)(SePh)]˙. After reorientation in the solvent cage, the radicals interact to form triplet adducts [MIIIMe2(bipy)(SePh)·(bipy)MIIIMe2(SePh)]˙˙ with π-stacked 'SePh·bipy', followed by transformation via a Minimum Energy Crossing Point allowing [SePh]˙ transfer to give MIIMe2(bipy) and MIVMe2(bipy)(SePh)2. The regenerated MII reagent reacts with Ph2Se2 through the above sequence, allowing completion of reaction to give the MIV product only. The reaction of PtMe2(bipy) with diphenyldisulfide has been studied in an analogous manner to assist with interpretation of DFT results for reactions of diphenyldiselenide. In short, this study shows that photochemical cleavage of metal-metal bonds (Pd, Pt) via excitation to an M-M antibonding orbital facilates disproportionation of the MIII-MIII complex to MII and MIV complexes.

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 Organoplatinum(IV) Chemistry: Dimers and Polymers Formed by Intermolecular Hydrogen Bonding.

The reaction of [PtMe2(6-dppd)], 1, where 6-dppd is a 1,4-bis(2-pyridyl)pyridazine derivative, with bromoalkanes BrCH2R, having a hydrogen-bond donor group R, gave the corresponding chiral products of trans oxidative addition [PtBrMe2(CH2R)(6-dppd)], 2a, R = CO2H; 3, R = 4-C6H4CO2H; 4, R = 4-C6H4CH2CO2H; 7, R = 2-C6H4CH2OH; 8, R = 4-C6H4B(OH)2; 9, R = 3-C6H4B(OH)2; and 10, R = 2-C6H4B(OH)2. Complex 2a was formed in equilibrium with two isomers formed by cis oxidative addition, while the reaction of 1 with BrCH2CH2CO2H gave mostly [PtBrMe(6-dppd)], 6. The supramolecular chemistry was studied by structure determination of six of the platinum(IV) complexes, with emphasis on the preference of the hydrogen bond acceptor (O, pyridyl N, or Br atom), formation of monomer, dimer, or polymer, and self-recognition or self-discrimination in self-assembly. Complex 7 formed a monomer with the OH···N hydrogen bond, and complexes 2a and 10 formed racemic dimers by complementary hydrogen bonding with self-discrimination between CO2H or B(OH)2 groups, respectively. Complexes 3, 4, and 9 formed polymers by intermolecular hydrogen bonding with self-recognition, with 4 containing OH···N and 3 and 9 containing OH···Br hydrogen bonds. It is concluded that there is no clear preference for the hydrogen bond acceptor group, and that the observed product depends also on the orientation of the hydrogen bond donor group.

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.

Photoswitchable and pH responsive organoplatinum(ii) complexes with azopyridine ligands.

Several platinum(ii) complexes with ligands containing azo groups have been prepared and structurally characterised, and their photoswitching between trans and cis azo group isomers has been studied. The azo groups in the cationic complexes [PtMe(bipy)(4-NC5H4-N[double bond, length as m-dash]N-4-C6H4X)][PF6], X = H, OH or NMe2, and in the dicationic complex [Pt(bipy)(4-H2NC6H4-N[double bond, length as m-dash]N-C6H5)2][OTf]2 undergo trans to cis photoswitching on irradiation at 365 nm. The complex [PtMe(bipy)(4-NC5H4-N[double bond, length as m-dash]N-4-C6H4NMe)2][PF6] also exhibits a reversible halochromic effect on protonation to give the dicationic complex [PtMe(bipy)(4-NC5H4-NH[double bond, length as m-dash]N-4-C6H4NMe2]2+. The nature of the frontier orbitals in the platinum(ii) complexes depends on the charge on the complex and on the degree of metal-ligand π-bonding.

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.

A biomimetic phenol substituent effect on the reaction of a dimethylplatinum(ii) complex with oxygen: proton coupled electron transfer and multiple proton relay.

The complex [PtMe2({κ(2)-N,N-RN[double bond, length as m-dash]CH-2-C5H4N})] reacts with oxygen in acetone solution to give the platinum(iv) complex [Pt(OH)Me2{κ(3)-N,N,O-RNH-CH(2-C5H4N)(CH[double bond, length as m-dash]CMeO)}], when R = 2-C6H4OH, but not when R = Ph. It has been suggested that the phenol substituent plays two key biomimetic roles; firstly, in proton coupled electron transfer reactions in the activation of oxygen and hydroperoxide groups and, secondly, in proton relay from a methyl group of the coordinated acetone.

Binuclear platinum-iridium complexes: synthesis, reactivity and luminescence.

The chemistry of the heterobinuclear platinum-iridium complex [PtIr(CO)3(µ-dppm)2][PF6], 1, dppm = Ph2PCH2PPh2, is described. The reaction of a hydride with 1 gave [HPtIr(CO)2(µ-dppm)2], by displacement of the carbonyl ligand from platinum, while reaction of 1 with dihydrogen, hydrogen chloride or Ph2MeSiH gave the fluxional complex [PtIrH4(CO)(µ-dppm)2][PF6], [PtIrH2Cl2(CO)(µ-dppm)2][PF6], or [PtIrH(SiMePh2)(CO)2(µ-dppm)2][PF6], respectively, by oxidative addition at iridium. Complex 1 reacted, often regioselectively, with several alkynes to give the µ-η(1),η(1) bridging alkyne complexes [PtIr(µ-RCCR')(CO)2(µ-dppm)2][PF6], R = H, R' = Ph, 4-C6H4Me, CO2Me; R = Ph, R' = CO2Me; R = R' = CO2Me. The complex [PtIr(µ-HCC-4-C6H4Me)(CO)2(µ-dppm)2][PF6] reacted reversibly with CO to give [PtIr(µ-HCC-4-C6H4Me)(CO)3(µ-dppm)2][PF6] and [PtIr(CO)3(µ-dppm)2][PF6], 1. With HCl, [PtIr(µ-HCC-4-C6H4Me)(CO)2(µ-dppm)2][PF6] reacted to give [PtIrHCl(µ-HCC-4-C6H4Me)(CO)2(µ-dppm)2][PF6], by oxidative addition at iridium, and then the alkenylplatinum derivative [PtIrCl{HC=CH(4-C6H4Me)}(CO)2(µ-dppm)2][PF6]. [PtIr(µ-HCC-4-C6H4Me)(CO)2(µ-dppm)2][PF6] reacted slowly with dihydrogen to give 4-MeC6H4CH=CH2 and [PtIrH4(CO)(µ-dppm)2][PF6]. The complex [PtIr(µ-HCCPh)(CO)2(µ-dppm)2][PF6] is intensely luminescent in solution at room temperature, with features characteristic of a d(8)-d(8) face-to-face complex.

3-Bromo-N-(3,5-di-tert-butyl-phen-yl)propanamide.

The title compound, C17H26BrNO, exhibits a small twist between the amide residue and the benzene ring [C-N-C-C torsion angle = 29.4 (5)°]. In the crystal, the amido NH group is involved in N-H⋯O hydrogen bonding, which connects mol-ecules into chains parallel to the c axis.

A versatile diphosphine ligand: cis and trans chelation or bridging, with self association through hydrogen bonding.

The diphosphine ligand, N,N'-bis(2-diphenylphosphinoethyl)isophthalamide, dpipa, contains two amide groups and can form cis or trans chelate complexes or cis,cis or trans,trans bridged complexes. The amide groups are likely to be involved in intramolecular or intermolecular hydrogen bonding. This combination of properties of the ligand dpipa leads to very unusual structural properties of its complexes, which often exist as mixtures of monomers and dimers in solution. In the complex [Au2(µ-dpipa)2]Cl2, the ligands adopt the trans,trans bridging mode, with linear gold(I) centers, and the amide groups hydrogen bond to the chloride anions. In [Pt2Cl4(µ-dpipa)2], the ligands adopt the cis,cis bridging mode, with square planar platinum(II) centers, and the amide groups form intermolecular hydrogen bonds to the chloride ligands to form a supramolecular one-dimensional polymer. Both the monomeric and dimeric complexes [PtMe2(dpipa)] and [Pt2Me4(µ-dpipa)2] have cis-PtMe2 units with cis chelating or cis,cis bridging dpipa ligands respectively; each forms a supramolecular dimer through hydrogen bonding between amide groups and each contains an unusual NH···Pt interaction. An attempted oxidative addition reaction with methyl iodide gave the complex [PtIMe(dpipa)], which contains trans chelating dpipa, while a reaction with bromine gave a disordered complex with approximate composition [Pt2Me3Br5(µ-dpipa)2], which contains trans,trans bridging dpipa ligands.

Easy activation of the aryl-sulfur bond by platinum(II).

The reagents 1,2-C6H4(CH=NR)(SMe), R = CH2CH2NMe2 or Ph, react with [Pt2Me4(µ-SMe2)2] by oxidative addition of the aryl-sulfur bond to give the corresponding crystalline binuclear platinum(IV) compounds [Pt2Me4(µ-SMe)2(κ(2)-C,N-C6H4-2-CH=NR)2], as the isomers with Ci (R = CH2CH2NMe2 or Ph) or C1 (R = Ph) symmetry. These first examples of C-S bond activation at platinum(II) occur easily at room temperature, and the reactions give complex equilibria of isomeric products, from which the isolated compounds crystallise.

Oxidation of dimethylplatinum(II) complexes with a peroxyacid.

The complexes [PtMe2(NN)], NN = 2,2'-bipyridine = bipy, 1a; NN = di-2-pyridylamine = dpa, 1b; NN = di-2-pyridyl ketone = dpk, 1c, NN = 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine, bebipy, react with m-chloroperoxybenzoic acid to give the platinum(IV) complexes [Pt(OH)(O2C-3-C6H4Cl)Me2(NN)], NN = bipy, 2, or [Pt(OH)(OH2···O2C-3-C6H4Cl)Me2(NN)], NN = bipy, 3a; dpa, 3b; bebipy, 3d, or [Pt(OH)2Me2(dpkOH)]3[Pt(OH)(OH2)Me2(dpkOH)][H(O2C-3-C6H4Cl)2]·2MeOH, 43·5·2MeOH. The reactions are proposed to occur by a polar oxidative addition mechanism, followed in most cases by the coordination of water. Complex 3a crystallises as a supramolecular polymer, the compound 43·5·2MeOH crystallises as a supramolecular sheet structure, and 3d easily forms a gel, all through strong intermolecular hydrogen bonding.

Self-assembly of isomeric clamshell dimers of platinum(II).

The controlled synthesis of isomeric organoplatinum clamshell dimers [Pt(2)Me(2)(µ(2)-κ(3)-6-dppd)(2)](2+), 6-dppd = 1,4-di-2-pyridyl-5,6,7,8,9,10-hexahydrocycloocta[d]pyridazine, is reported. The new complexes are formed selectively by self-assembly from mononuclear precursors, taking advantage of the slow cis-trans isomerization at platinum(II). Thus reaction of endo-[PtClMe(κ(2)-6-dppd)] with AgOTf gave endo,endo-[Pt(2)Me(2)(µ(2)-κ(3)-6-dppd)(2)](2+), while the reaction of [PtMe(2)(κ(2)-6-dppd)] with HOTf in solvent S = Me(2)C=O or MeCN gave first a mixture of exo- and endo-[PtMe(S)(κ(2)-6-dppd)](+) and then, by loss of solvent, a mixture of exo,exo- and endo,endo-[Pt(2)Me(2)(µ(2)-κ(3)-6-dppd)(2)](2+). The endo,endo isomer slowly isomerized to the more stable exo,exo isomer in solution. Reaction of PPh(3) with endo-[PtClMe(κ(2)-6-dppd)] gave a mixture of endo- and exo-[PtMe(PPh(3))(κ(2)-6-dppd)](+) but reaction with exo,exo-[Pt(2)Me(2)(µ(2)-κ(3)-6-dppd)(2)](2+) gave exo-[PtMe(PPh(3))(κ(2)-6-dppd)](+) selectively, with retention of stereochemistry. The structures of the clamshell dimers and of key precursors are reported and equilibria are studied both experimentally and by DFT calculations.