Ola F. Wendt

Insertion of CO2 into a palladium allyl bond and a Pd(II) catalysed carboxylation of allyl stannanes

The complex 2,6-bis[(di-t-butylphosphino)methyl]phenyl allyl palladium (PCP(tBu)Pd-allyl, 3) reacts with CO(2) in a very fast insertion reaction to give the corresponding butenoate complex. The reaction is thought to occur via a cyclic six-membered transition state (7), where the gamma-carbon of the allyl group is linked up with the CO(2)-carbon. A group of related PCP complexes were investigated as catalysts for the carboxylation of tributyl(allyl)stannane. A catalytic cycle is proposed for this reaction where the rate determining step is the transmetallation between tin and palladium. The carboxylation reaction is faster using less sterically crowded catalysts whereas the electron richness of the palladium complexes seems less important for reactivity. Thus, there was no apparent difference in reactivity between 2,6-bis[(di-phenylphosphino)methyl]phenyl palladium triflouroacetate (13) and resorcinolbis(diphenyl)phosphinite palladium triflouroacetate (10). Both of these complexes give high turnovers for the carboxylation of tributyl(allyl)stannane (80% in 16 h using a ca. 5% catalyst loading and 4 atm CO(2) pressure). On the other hand complex 3 was inactive in the catalytic carboxylation reaction.

Neutral Organometallic Halogen Bond Acceptors: Halogen Bonding in Complexes of PCPPdX (X = Cl, Br, I) with Iodine (I(2)), 1,4-Diiodotetrafluorobenzene (F4DIBz), and 1,4-Diiodooctafluorobutane (F8DIBu).

The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I2), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl–I2 (1a), PCPPdBr–I2 (2a), PCPPdI–I2(3a), PCPPdCl–F4DIBz (1b), PCPPdBr–F4DIBz (2b), and PCPPdBr–F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine being 24.6 (1a), 23.9 (2a), and 19.4% (3a) with X···I–I angles of 177, 176, and 179°, respectively. While the pincer palladium chloride 1 and bromide 2 were crystallographically isomorphous and showed similar XB behavior, the palladium iodide complex, 3, exhibited markedly different properties, and unlike 1 and 2 it does not, under similar conditions, result in XB complexes with the weaker XB donors F4DIBz and F8DIBu. The results indicate that PCPPdI is not nucleophilic enough to have XB interactions with other donors than iodine. However, the weaker XB donors F4DIBz and F8DIBu form XB complexes with the chloride 1 and especially with the bromide 2. The prevalence of the halogen bonding with 2 is probably not only electronic in origin, and it seems to offer the best balance between electron poorness and steric availability. The XB interactions with F4DIBz and F8DIBu are much weaker than with iodine, the reduction of the sum of the van der Waals radii of halogen to iodine being 13.5, 12.3, and 14.6% with C–I···X angles between 163 and 179° for 1b, 2b, and 2c, respectively, and results in polymeric (···1···F4DIBz···1···F4DIBz···)n, (···2···F4DIBz···2···F4DIBz···)n, and (···2···F8DIBu···2···F8DIBu···)n one-dimensional zigzag chains in the solid state.

Trans influence of triphenylstibine. Crystal and molecular structures of cis-[PtCl2(SbPh3)2] and trans-[PtI2(SbPh3)2]

Crystals of cis-[PtCl2(SbPh3)2] (1) are monoclinic, space group . Substitution of chloride for iodide yields trans-[PtI2(SbPh3)2] (2), the crystals of which are monoclinic, space group . The average PtCl distance in 1 is 2.338(12) A, implying a trans influence of triphenyl stibine comparable with that of triphenyl phosphine, as opposed to what has been reported earlier. IR and Raman data for 1 and 2 are reported and discussed.

Synthesis and characterisation of PCsp3P phosphine and phosphinite iridium complexes. Cyclometallation and dehydrogenation of a cyclohexyl ring

A cyclohexyl based pincer phosphine ligand undergoes cyclometalation with an iridium cyclooctadiene precursor to give a highly thermally stable iridium(III) complex where a C(sp3)-H bond has been oxidatively added. This iridium(III) hydride complex is reduced with potassium to give a terminal iridium(I) dinitrogen complex with no tendency to dimerization. The corresponding cyclohexyl phosphinite ligand undergoes reversible dehydrogenation to give the aromatic cyclometalated iridium(III) hydride complex together with 3 equivalents of dihydrogen.

Synthesis and Characterization of a Family of POCOP Pincer Complexes with Nickel: Reactivity Towards CO2 and Phenylacetylene

A cyclohexyl-based POC sp 3OP pincer ligand (POC sp 3OP=cis-1,3-bis(di-tert-butylphosphinito)cyclohexyl) cyclometalates with nickel to generate a series of new POC sp 3OP-supported Ni(II) complexes, including the halide, hydride, methyl, and phenyl species. trans-[NiCl{cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}], [(POC sp 3OP)NiCl] (1 a) and the analogous bromide complex (1 b) were synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of 1 a and 1 b alongside their bis(phosphine) analogues [(PC sp 3P)NiCl] (2 a) and [(PC sp 3P)NiCl] (2 a) (PC sp 3P=cis-1,3-bis(di-tert-butylphosphino)cyclohexyl) indicate a reduced electron density at the metal center upon introducing electron-withdrawing oxygen atoms in the pincer arms. The methyl [(POC sp 3OP)NiMe] (3) and phenyl [(POC sp 3OP)NiPh] (4) complexes were formed from 1 a by reaction with the corresponding organolithium reagents. 1 a also reacts with LiAlH4 to give the hydride complex [(POC sp 3OP)NiH] (5). The methyl complex 3 reacts with phenyl acetylene to give the acetylide complex [(POC sp 3OP)NiCCPh] (6). The reactivity of compounds 3-5 towards CO2 was studied. The hydride complex 5 and the methyl complex 3 both underwent CO2 insertion to form the formate species [(POC sp 3OP)NiOCOH] (7) and acetate species [(POC sp 3OP)NiOCOCH3 ] (8), respectively, although with a higher barrier of insertion in the latter case. Compound 4 was unreactive towards CO2 even at elevated temperatures. Complexes 3-8 were all characterized by NMR spectroscopy and X-ray crystallography.

Twisted Amide Analogues of Tröger’s Base

Lets do the twist: The first twisted bis-amide is obtained by the benzylic oxidation of Trogers base (TB). Kinetic studies of its acidic hydrolysis reveal that the hydrolysis is to a large extent funneled through doubly protonated species.

Reversible α-Hydrogen and α-Alkyl Elimination in PC(sp(3) )P Pincer Complexes of Iridium.

Despite significant progress in recent years, the cleavage of unstrained C(sp(3))-C(sp(3)) bonds remains challenging. A C-C coupling and cleavage reaction in a PC(sp(3))P iridium pincer complex is mechanistically studied; the reaction proceeds via the formation of a carbene intermediate and can be described as a competition between α-hydrogen and α-alkyl elimination; the latter process was observed experimentally and is an unusual way of C(sp(3))-C(sp(3)) bond scission, which has previously not been studied in detail. Mechanistic details that are based upon kinetic studies, activation parameters, and DFT calculations are also discussed. A full characterization of a C-C agostic intermediate is presented.

Improved arsenic(III) adsorption by Al2O3 nanoparticles and H2O2: Evidence of oxidation to arsenic(V) from X-ray absorption spectroscopy

We have investigated the oxidation of inorganic As(III) with H2O2 catalysed by Al2O3, using X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. The effects of different reaction conditions (pH, time and initial H2O2 concentration) were also studied as were the kinetics of the oxidation reaction. We demonstrated that As(III) was oxidized to As(V) in the presence of H2O2 and Al2O3. Furthermore, all arsenic species found on the Al2O3 surface were in the As(V) state. The presence of both Al2O3 and H2O2 was necessary for oxidation of As(III) to take place within the period of time studied. The oxidation kinetics indicate a mechanism where reversible As(III) binding to the alumina surface is followed by irreversible oxidation by H2O2 leading to strongly bound As(V). Results from this study indicate that there is a surface-catalysed oxidation of As(III) on Al2O3 by H2O2, a reaction that can take place in nature and can be of help in the development of novel treatment systems for As(III) removal.

Synthesis and self-aggregation of enantiopure and racemic molecular tweezers based on the bicyclo[3.3.1]nonane framework.

A pair of molecular tweezers (syn-4) that consists of quinoline and pyrazine units fused to a bicyclic framework is presented. The tweezers were synthesised both as a racemic mixture (rac-4) and an enantiomerically pure form ((R,R,R,R)-4) starting from either racemic or enantiomerically pure bicyclo[3.3.1]nonane-2,6-dione (3). Homochiral dimers were observed in the solid state for rac-4. The self-association of both rac-4 and (R,R,R,R)-4 was studied in solution. A weak self-association constant in CDCl(3) was estimated by (1)H NMR spectroscopic dilution titration experiments in both cases, following several proton resonances. For this purpose, a general normalisation model for the accurate determination of association constants from multiple datasets was developed. In contrast to the solid state, no diastereomeric discrimination was observed for rac-4 in solution.

Trinorsesquiterpenoids from the Root Extract of Pentalinon andrieuxii

Two unusual trinorsesquiterpenoids, urechitols A (1) and B (2), were isolated from the root extract of Pentalinon andrieuxii, a plant used commonly in Yucatecan traditional medicine to treat leishmaniasis. The structures of 1 and 2 were identified by interpretation of their spectroscopic data and chemical correlation reactions. The relative stereochemistry of 1 was confirmed through an X-ray crystallographic study.