Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide

Structure-function studies on the role of pendent Lewis acids in the reductive coupling of CO are reported. Cationic rhenium carbonyl complexes containing zero, one, or two phosphinoborane ligands (Ph_2P(CH_2)_nB(C_8H_(14)), n=1-3) react with the nucleophilic hydride [HPt(dmpe)_2]^+ to reduce [M-CO]^+ to M-CHO; this step is relatively insensitive to the Lewis acid, as both pendent (internal) and external boranes of appropriate acid strength can be used. In contrast, whether a second hydride transfer and C-C bond forming steps occur depends strongly on the number of carbon atoms between P and B in the phosphinoborane ligands, as well as the number of pendent acids in the complex: shorter linker chain lengths favor such reductive coupling, whereas longer chains and external boranes are ineffective. A number of different species containing partially reduced CO groups, whose exact structures vary considerably with the nature and number of phosphinoborane ligands, have been crystallographically characterized. The reaction of [(Ph -2P(CH_2)_2B(C_8H_(14)))_2Re(CO)4]^+ with [HPt(dmpe)_2]^+ takes place via a “hydride shuttle” mechanism, in which hydride is transferred from Pt to a pendent borane and thence to CO, rather than by direct hydride attack at CO. Addition of a second hydride in C_6D_5Cl at -40 ºC affords an unusual anionic bis(carbene) complex, which converts to a C-C bonded product on warming. These results support a working model for Lewis acid-assisted reductive coupling of CO, in which B (pendent or external) shuttles hydride from Pt to coordinated CO, followed by formation of an intramolecular B-O bond, which facilitates reductive coupling

Trialkylborane-Assisted CO_2 Reduction by Late Transition Metal Hydrides

Trialkylborane additives promote reduction of CO_2 to formate by bis(diphosphine) Ni(II) and Rh(III) hydride complexes. The late transition metal hydrides, which can be formed from dihydrogen, transfer hydride to CO_2 to give a formateborane adduct. The borane must be of appropriate Lewis acidity: weaker acids do not show significant hydride transfer enhancement, while stronger acids abstract hydride without CO_2 reduction. The mechanism likely involves a pre-equilibrium hydride transfer followed by formation of a stabilizing formateborane adduct

Homogeneous CO Hydrogenation: Dihydrogen Activation Involves a Frustrated Lewis Pair Instead of a Platinum Complex

During a search for conditions appropriate for Pt-catalyzed CO reduction using dihydrogen directly, metal-free conditions were discovered instead. A bulky, strong phosphazene base forms a “frustrated” Lewis pair (FLP) with a trialkylborane in the secondary coordination sphere of a rhenium carbonyl. Treatment of the FLP with dihydrogen cleanly affords multiple hydride transfers and C−C bond formation

21st century innovation: What is the name of the new game?

This is the author accepted manuscrip. The final version is available from ISPIM via the link in this recordThe Circular Economy is a relatively immature research landscape, particularly when considered from an Innovation perspective. However it is gaining momentum and according to critics offers a solution to many of the issues currently being experienced around the world, in terms of resource shortages and the energy, food, water nexus. This study attempts to explore examples of products and services, collected by the Ellen MacArthur Foundation, to begin to understand which size of companies are developing them, what types of innovations they represent and how they might diffuse to scale. The contribution of this paper is to introduce, define and raise awareness of circular innovations whilst beginning to articulate how analysis of CE products and service might be undertaken by further studies, with the aim of informing companies and policy-makers accordingly

Synthesis and C−C Coupling Reactivity of a Dinuclear Ni^I−Ni^I Complex Supported by a Terphenyl Diphosphine

Mono- and bimetallic complexes of nickel supported by a terphenyl diphosphine have been synthesized. The reported complexes show diverse metal−arene interactions in the solid state. Reactions of an o,o′-biphenyldiyl dinickel complex with CO and dichloroalkanes lead to fluorene derivatives, indicating the formation of carbon−carbon bonds at a bimetallic moiety

A Two-Coordinate Nickel Imido Complex That Effects C−H Amination

An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4)

Alloreactive cytotoxic T lymphocytes generated in the presence of viral- derived peptides show exquisite peptide and MHC specificity

The nature of alloreactivity to MHC molecules has been enigmatic, primarily because of the observation that allogeneic responses are considerably stronger than syngeneic responses. To better determine the specificity potential of allogeneic responses, we have generated alloreactive CTL specific for exogenous, viral-derived peptide ligands. This approach allowed us to critically evaluate both the peptide- and MHC-specificity of these alloreactive T cells. Exploiting the accessibility of the H-2Ld class I molecule for exogenous peptide ligands, alloreactive CTL were generated that are specific for either murine cytomegalovirus (MCMV) or lymphocytic choriomeningitis virus (LCMV) peptides bound by Ld alloantigens. Peptide specificity was initially observed in bulk cultures of alloreactive CTL only when tested on peptide-sensitized T2.Ld target cells that have defective presentation of endogenous peptides. Subsequent cloning of bulk alloreactive CTL lines generated to MCMV yielded CTL clones that had exquisitely specific MCMV peptide recognition requirement. All of the MCMV/Ld alloreactive CTL clones were also exquisitely MHC-specific in that none of the CTL clones lysed targets expressing MCMV/Lq complexes, even though Lq differs from Ld by only six amino acid residues and Lq also binds the MCMV peptide. This observation clearly demonstrates that alloreactive CTL are capable of the same degree of specificity for target cell recognition as are syngeneic CTL in MHC-restricted responses

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes

A new family of low-coordinate nickel imides supported by 1,2-bis(di-tert-butylphosphino)ethane was synthesized. Oxidation of nickel(II) complexes led to the formation of both aryl- and alkyl-substituted nickel(III)-imides, and examples of both types have been isolated and fully characterized. The aryl substituent that proved most useful in stabilizing the Ni(III)-imide moiety was the bulky 2,6-dimesitylphenyl. The two Ni(III)-imide compounds showed different variable-temperature magnetic properties but analogous EPR spectra at low temperatures. To account for this discrepancy, a low-spin/high-spin equilibrium was proposed to take place for the alkyl-substituted Ni(III)-imide complex. This proposal was supported by DFT calculations. DFT calculations also indicated that the unpaired electron is mostly localized on the imide nitrogen for the Ni(III) complexes. The results of reactions carried out in the presence of hydrogen donors supported the findings from DFT calculations that the adamantyl substituent was a significantly more reactive hydrogen-atom abstractor. Interestingly, the steric properties of the 2,6-dimesitylphenyl substituent are important not only in protecting the Ni═N core but also in favoring one rotamer of the resulting Ni(III)-imide, by locking the phenyl ring in a perpendicular orientation with respect to the NiPP plane

Thermodynamic Studies of [H_(2)Rh(diphosphine)_2]^+ and [HRh(diphosphine)_(2)(CH_(3)CN)]^(2+) Complexes in Acetonitrile

Thermodynamic studies of a series of [H_(2)Rh(PP)_2]^+ and [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes have been carried out in acetonitrile. Seven different diphosphine (PP) ligands were selected to allow variation of the electronic properties of the ligand substituents, the cone angles, and the natural bite angles (NBAs). Oxidative addition of H_2 to [Rh(PP)_2]^+ complexes is favored by diphosphine ligands with large NBAs, small cone angles, and electron donating substituents, with the NBA being the dominant factor. Large pK_a values for [HRh(PP)_(2)(CH_(3)CN)]^(2+) complexes are favored by small ligand cone angles, small NBAs, and electron donating substituents with the cone angles playing a major role. The hydride donor abilities of [H_(2)Rh(PP)_2]^+ complexes increase as the NBAs decrease, the cone angles decrease, and the electron donor abilities of the substituents increase. These results indicate that if solvent coordination is involved in hydride transfer or proton transfer reactions, the observed trends can be understood in terms of a combination of two different steric effects, NBAs and cone angles, and electron-donor effects of the ligand substituents