Optimised graphite/carbon black loading of recycled PLA for the production of low-cost conductive filament and its application to the detection of ß-estradiol in environmental samples.

The production, optimisation, physicochemical, and electroanalytical characterisation of a low-cost electrically conductive additive manufacturing filament made with recycled poly(lactic acid) (rPLA), castor oil, carbon black, and graphite (CB-G/PLA) is reported. Through optimising the carbon black and graphite loading, the best ratio for conductivity, low material cost, and printability was found to be 60% carbon black to 40% graphite. The maximum composition within the rPLA with 10 wt% castor oil was found to be an overall nanocarbon loading of 35 wt% which produced a price of less than £0.01 per electrode whilst still offering excellent low-temperature flexibility and reproducible printing. The additive manufactured electrodes produced from this filament offered excellent electrochemical performance, with a heterogeneous electron (charge) transfer rate constant, k0 calculated to be (2.6 ± 0.1) × 10-3 cm s-1 compared to (0.46 ± 0.03) × 10-3 cm s-1 for the commercial PLA benchmark. The additive manufactured electrodes were applied to the determination of ß-estradiol, achieving a sensitivity of 400 nA µM-1, a limit of quantification of 70 nM, and a limit of detection of 21 nM, which compared excellently to other reports in the literature. The system was then applied to the detection of ß-estradiol within four real water samples, including tap, bottled, river, and lake water, where recoveries between 95 and 109% were obtained. Due to the ability to create high-performance filament at a low material cost (£0.06 per gram) and through the use of more sustainable materials such as recycled polymers, bio-based plasticisers, and naturally occurring graphite, additive manufacturing will have a permanent place within the electroanalysis arsenal in the future.

The borylamino-diborata-allyl anion.

Reactions of ß-diketiminato alkaline earth alkyldiboranate derivatives [(BDI)Ae{pinBB(R)pin}] (BDI = HC{(Me)CNDipp}2; Dipp = 2,6-i-Pr2C6H3; Ae = Mg, R = n-Bu or Ae = Ca, R = n-hexyl) with t-BuNC provide access to the respective group 2 derivatives of unprecedented diborata-allyl, {(pinB)2CNBpin(t-Bu)}-, anions. Although the necessary mode of B-C bond cleavage implicated in these transformations could not be elucidated, further studies of the reactivity of magnesium triboranates toward isonitriles delivered a more general and rational synthetic access to analogous anionic moieties. Extending this latter reactivity to a less symmetric triboranate variant also provided an isomeric Mg-C-bonded dibora-alkyl species and sufficient experimental insight to prompt theoretical evaluation of this reactivity. DFT calculations, thus, support a reaction pathway predicated on initial RNC attack at a peripheral boron centre and the intermediacy of such dibora-alkyl intermediates.

Highly selective, reversible water activation by P,N-cooperativity in pyridyl-functionalized phosphinines.

Tetrapyridyl-functionalized phosphinines were prepared and structurally characterized. The donor-functionalized aromatic phosphorus heterocycles react highly selectively and even reversibly with water. Calculations reveal P,N-cooperativity for this process, with the flanking pyridyl groups serving to kinetically enhance the formal oxidative addition process of H2O to the low-coordinate phosphorus atom via H-bonding. Subsequent tautomerization forms 1,2-dihydrophosphinine derivatives, which can be quantitatively converted back to the phosphinine by applying vacuum, even at room temperature. This process can be repeated numerous times, without any sign of decomposition of the phosphinine. In the presence of CuI·SMe2, dimeric species of the type ([Cu2I2(phosphinine)]2) are formed, in which each phosphorus atom shows the less common µ2-bridging 2e--lone-pair-donation to two Cu(i)-centres. Our results demonstrate that fully unsaturated phosphorus heterocycles, containing reactive P[double bond, length as m-dash]C double bonds, are interesting candidates for the activation of E-H bonds, while the aromaticity of such compounds plays an appreciable role in the reversibility of the reaction, supported by NICS calculations.

[{SiNDipp}MgNa]2: A Potent Molecular Reducing Agent.

The bimetallic species, [{SiNDipp}MgNa]2 [{SiNDipp} = {CH2SiMe2N(Dipp)}2; (Dipp = 2,6-i-Pr2C6H3)], is shown to be a potent reducing agent, able to effect one- or two-electron reduction of either dioxygen, TEMPO, anthracene, benzophenone, or diphenylacetylene. In most cases, the bimetallic reaction products imply that the dissimilar alkaline metal centers react with a level of cooperativity. EPR analysis of the benzophenone-derived reaction and the concurrent isolation of [{SiNDipp}Mg(OCPh2)2], however, illustrate that treatment with such reducible, but O-basic, species can also result in reactivity in which the metals provide independent reaction products. The notable E-stereochemistry of the diphenylacetylene reduction product prompted a computational investigation of the PhC≡CPh addition. This analysis invokes a series of elementary steps that necessitate ring-opening via Mg+ → Na+ amido group migration of the SiNDipp ligand, providing insight into the previously observed lability of the bidentate dianion and its consequent proclivity toward macrocyclization.

The structures and reactivity of NHC-supported copper(i) triphenylgermyls.

Deprotonation of triphenyl germane with NHC-supported copper alkoxides afforded four novel (NHC)CuGePh3 complexes. Of these, (IPr)CuGePh3 (IPr = :C{N(2,6-iPr2C6H3)CH}2) was selected for further investigation. Analysis by EDA-NOCV indicates it to be a germyl nucleophile and its σ-bond metathesis reaction with a range of p-block halides confirmed it to be a convenient source of [Ph3Ge]-. The Cu-Ge bond of (IPr)CuGePh3 underwent π-bond insertions with tBuNCS, CS2, and PhNCO to furnish a series of germyl substituted carboxylate derivatives, (IPr)CuXC(Y)GePh3 (X = S, NPh; Y = S, NtBu, O), which were structurally characterised. (IPr)CuGePh3 inserted phenyl acetylene, providing both the Markovnikov and anti-Markovnikov products. The (NHC)CuGePh3 compounds were validated as catalytic intermediates; addition of 10 mol% of NHC-copper(i) alkoxide to a mixture of triphenyl germane and a tin(iv) alkoxide resulted in a tin/germanium cross coupling with concomitant formation of alcohol. Moreover, a catalytic hydrogermylation of Michael acceptors was developed with Ph3GeH adding to 7 activated alkenes in good conversions and yields in the presence of 10 mol% of NHC-copper(i) alkoxide. In all cases, this reaction provided the ß-germylated substrate implicating nucleophilicity at germanium.

Acyclic Boryl Complexes of Copper(I).

Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH2 }2 CH2 , Dipp=2,6-iPr2 C6 H3 ) with B2 (OMe)4 provided access to (6-Dipp)CuB(OMe)2 via σ-bond metathesis. (6-Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2 (OMe)4 . Alongside π-insertion, (6-Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe2 , a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.

Alkali metal reduction of alkali metal cations.

Counter to synthetic convention and expectation provided by the relevant standard reduction potentials, the chloroberyllate, [{SiNDipp}BeClLi]2 [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3)], reacts with the group 1 elements (M = Na, K, Rb, Cs) to provide the respective heavier alkali metal analogues, [{SiNDipp}BeClM]2, through selective reduction of the Li+ cation. Whereas only [{SiNDipp}BeClRb]2 is amenable to reduction by potassium to its nearest lighter congener, these species may also be sequentially interconverted by treatment of [{SiNDipp}BeClM]2 by the successively heavier group 1 metal. A theoretical analysis combining density functional theory (DFT) with elemental thermochemistry is used to rationalise these observations, where consideration of the relevant enthalpies of atomisation of each alkali metal in its bulk metallic form proved crucial in accounting for experimental observations.

Cooperative dihydrogen activation at a Na(I)2/Mg(I)2 ensemble.

[{SiNDipp}MgNa]2 ({SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3) reacts directly with H2 to provide a heterobimetallic hydride. Although the transformation is complicated by the simultaneous disproportionation of magnesium, computational density functional theory (DFT) studies suggest that this reactivity is initiated by orbitally-constrained and interactions between the frontier MOs of both H2 and the tetrametallic core of [{SiNDipp}MgNa]2.

Structural snapshots of an Al-Cu bond-mediated transformation of terminal acetylenes.

The copper(i) alumanyl derivative, [{SiNDipp}Al-Cu(NHCiPr)] (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-di-isopropylphenyl; NHCiPr = N,N'-di-isopropyl-4,5-dimethyl-2-ylidene), reacts in a stepwise fashion with up to three equivalents of various terminal alkynes. This reactivity results in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate and bis(alkynyl)aluminate derivatives, examples of which have been fully characterised. The process of alkene liberation resulting from the latter reaction step constitutes a unique case of alkyne transfer semi-hydrogenation in which the C-H acidic alkyne itself acts as a source of proton, with the Cu-Al bond providing the requisite electrons to effect reduction. This reaction sequence is validated by DFT calculations, which rationalise the variable stability of the initially formed heterobimetallic hydrides.

Exploring the Role of the Connection Length of Screen-Printed Electrodes towards the Hydrogen and Oxygen Evolution Reactions.

Zero-emission hydrogen and oxygen production are critical for the UK to reach net-zero greenhouse gasses by 2050. Electrochemical techniques such as water splitting (electrolysis) coupled with renewables energy can provide a unique approach to achieving zero emissions. Many studies exploring electrocatalysts need to "electrically wire" to their material to measure their performance, which usually involves immobilization upon a solid electrode. We demonstrate that significant differences in the calculated onset potential for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be observed when using screen-printed electrodes (SPEs) of differing connection lengths which are immobilized with a range of electrocatalysts. This can lead to false improvements in the reported performance of different electrocatalysts and poor comparisons between the literature. Through the use of electrochemical impedance spectroscopy, uncompensated ohmic resistance can be overcome providing more accurate Tafel analysis.

Selective hydroboration of electron-rich isocyanates by an NHC-copper(I) alkoxide.

The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane gave only the boraformamides, pinBN(R)C(O)H, in most cases. Overreduction, which hampers almost all isocyanate hydroborations, was restricted to electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis showed stability of [(IPr)CuH]2, which was proposed to be the catalyst resting state, drives selectivity, suggesting an approach to prevent overreduction in future work. In the case of iPrNCO, formation of this species renders overreduction kinetically inaccessible. For 4-NC-C6H4NCO, however, the barrier height for the first step of over-reduction is much lower, even relative to [(IPr)CuH]2, resulting in unselective reduction.

Reduction of Na+ within a {Mg2 Na2 } Assembly.

Ionic compounds containing sodium cations are notable for their stability and resistance to redox reactivity unless highly reducing electrical potentials are applied. Here we report that treatment of a low oxidation state {Mg2 Na2 } species with non-reducible organic bases induces the spontaneous and completely selective extrusion of sodium metal and oxidation of the MgI centers to the more conventional MgII state. Although these processes are also characterized by a structural reorganisation of the initially chelated diamide spectator ligand, computational quantum chemical studies indicate that intramolecular electron transfer is abetted by the frontier molecular orbitals (HOMO/LUMO) of the {Mg2 Na2 } ensemble, which arise exclusively from the 3s valence atomic orbitals of the constituent sodium and magnesium atoms.

Triple dehydrofluorination as a route to amidine-functionalized, aromatic phosphorus heterocycles.

An unexpected route to hitherto unknown amidine-functionalized phosphinines has been developed that is rapid and simple. Starting from primary amines and CF3-substituted λ3,σ2-phosphinines, a cascade of dehydrofluorination reactions leads selectively to ortho-amidinephosphinines. DFT calculations reveal that this unusual transformation can take place via a series of nucleophilic attacks at the electrophilic, low-coordinate phosphorus atom.

Isolating elusive 'Al(µ-O)M' intermediates in CO2 reduction by bimetallic Al-M complexes (M = Zn, Mg).

The reaction of compounds containing Al-Mg and Al-Zn bonds with N2O enabled isolation of the corresponding Al(µ-O)M complexes. Electronic structure analysis identified largely ionic Al-O and O-M bonds, featuring an anionic µ-oxo centre. Reaction with CO2 confirmed that these species correspond to the proposed intermediates in the formation of µ-carbonate compounds.

Carbon-chalcogen bond formation initiated by [Al(NONDipp)(E)]- anions containing Al-E{16} (E{16} = S, Se) multiple bonds.

Multiply-bonded main group metal compounds are of interest as a new class of reactive species able to activate and functionalize a wide range of substrates. The aluminium sulfido compound K[Al(NONDipp)(S)] (NONDipp = [O(SiMe2NDipp)2]2-, Dipp = 2,6-iPr2C6H3), completing the series of [Al(NONDipp)(E)]- anions containing Al-E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed via desulfurisation of K[Al(NONDipp)(S4)] using triphenylphosphane. The crystal structure showed a tetrameric aggregate joined by multiple K⋯S and K⋯π(arene) interactions that were disrupted by the addition of 2.2.2-cryptand to form the separated ion pair, [K(2.2.2-crypt)][Al(NONDipp)(S)]. Analysis of the anion using density functional theory (DFT) confirmed multiple-bond character in the Al-S group. The reaction of the sulfido and selenido anions K[Al(NONDipp)(E)] (E = S, Se) with CO2 afforded K[Al(NONDipp)(κ2 E,O-EC{O}O)] containing the thio- and seleno-carbonate groups respectively, consistent with a [2 + 2]-cycloaddition reaction and C-E bond formation. An analogous cycloaddition reaction took place with benzophenone affording compounds containing the diphenylsulfido- and diphenylselenido-methanolate ligands, [κ2 E,O-EC{O}Ph2]2-. In contrast, when K[Al(NONDipp)(E)] (E = S, Se) was reacted with benzaldehyde, two equivalents of substrate were incorporated into the product accompanied by formation of a second C-E bond and complete cleavage of the Al-E{16} bonds. The products contained the hitherto unknown κ2 O,O-thio- and κ2 O,O-seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the cis-stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods.

2D-Hexagonal Boron Nitride Screen-Printed Bulk-Modified Electrochemical Platforms Explored towards Oxygen Reduction Reactions.

A low-cost, scalable and reproducible approach for the mass production of screen-printed electrode (SPE) platforms that have varying percentage mass incorporations of 2D hexagonal boron nitride (2D-hBN) (2D-hBN/SPEs) is demonstrated herein. These novel 2D-hBN/SPEs are explored as a potential metal-free electrocatalysts towards oxygen reduction reactions (ORRs) within acidic media where their performance is evaluated. A 5% mass incorporation of 2D-hBN into the SPEs resulted in the most beneficial ORR catalysis, reducing the ORR onset potential by ca. 200 mV in comparison to bare/unmodified SPEs. Furthermore, an increase in the achievable current of 83% is also exhibited upon the utilisation of a 2D-hBN/SPE in comparison to its unmodified equivalent. The screen-printed fabrication approach replaces the less-reproducible and time-consuming drop-casting technique of 2D-hBN and provides an alternative approach for the large-scale manufacture of novel electrode platforms that can be utilised in a variety of applications.

On the reactivity of Al-group 11 (Cu, Ag, Au) bonds.

Reactions of the seven-membered heterocyclic potassium diamidoalumanyl, [K{Al(SiNDipp)}]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-di-isopropylphenyl), with a variety of Cu(I), Ag(I) and Au(I) chloride N-heterocyclic carbene (NHC) adducts are described. The resultant group 11-Al bonded derivatives have been characterised in solution by NMR spectroscopy and, in the case of [{SiNDipp}Al-Au(NHCiPr)] (NHCiPr = N,N'-di-isopropyl-4,5-dimethyl-2-ylidene), by single crystal X-ray diffraction. Although similar reactions of LAgCl and LAuCl, where L is a more basic cyclic alkyl amino carbene (CAAC), generally resulted in reduction of the group 11 cations to the base metals, X-ray analysis of [(CyCAAC)AgAl(SiNDipp)] (CyCAAC = 2-[2,6-bis(1-methylethyl)phenyl]-3,3-dimethyl-2-azaspiro[4.5]dec-1-ylidene) provides the first solid-state authentication of an Ag-Al σ bond. The reactivity of the NHC-supported Cu, Ag and Au alumanyl derivatives was assayed with the isoelectronic unsaturated small molecules, N,N'-di-isopropylcarbodiimide and CO2. While these reactions generally provided products consistent with nucleophilic attack of the group 11 atom at the electrophilic heteroallene carbon centre, treatment of the NHC-supported copper and silver alumanyls with N,N'-di-isopropylcarbodiimide yielded less symmetric Cu-C and Ag-C-bonded isomers. In contrast to the previously described copper and silver alumanyl derivatives, [(NON)Al(O2C)M(Pt-Bu3)] (M = Cu or Ag; NON = 4,5-bis(2,6-di-isopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene), which were prone to facile CO extrusion and formation of carbonate derivatives, the NHC-supported dioxocarbene species, [(NHCiPr)M(CO2)Al(SiNDipp)] (M = Cu, Ag, Au), are all stable at room and moderately elevated temperatures. The stabilising role of the NHC co-ligand was, thus, assessed by preparation of the t-Bu3P adducted copper-alumanyl, [(t-Bu3P)CuAl(SiNDipp)]. Treatment of this latter compound, which was also structurally characterised by X-ray analysis, with both N,N'-di-isopropylcarbodiimide and CO2 again provided smooth heteroallene insertion and formation of the relevant Cu-C-bonded products. Although both compounds were quite stable at room temperature, heating of [(t-Bu3P)Cu(CO2)Al(SiNDipp)] at 60 °C induced elimination of CO and formation of the analogous carbonate, [(t-Bu3P)Cu(OCO2)Al(SiNDipp)], which was identified by 13C and 31P NMR spectroscopy. Reflective of the more reliable nucleophilic behaviour of the gold centres in these group 11 alumanyls, computational (QTAIM and NBO) analysis highlighted a lower level of covalency of the Al-Au linkage in comparison to the analogous Al-Cu and Al-Ag interactions. Although substitution of the co-ligand significantly perturbs the charge distribution across the Cu-Al bond of [LCuAl(SiNDipp)] (L = NHCiPr or t-Bu3P), only a negligible difference is observed between the phosphine-coordinated copper systems derived from either the [SiNDipp]- or (NON)-based alumanyl ligands. Computational mapping of the reaction profiles arising from treatment of the various group 11 alumanyls with N,N'-di-isopropylcarbodiimide indicates that the observed formation of the Cu-N and Ag-N bound isomers do not provide the thermodynamic reaction outcome. In contrast, examination of the CO2-derived reactions, and their potential toward CO extrusion and subsequent carbonate formation, implies that the identity of the co-ligand exerts a greater influence on this aspect of reactivity than the architecture of the diamidoalumanyl anion.

Potassium Aluminyl Promoted Carbonylation of Ethene.

The potassium aluminyl [K{Al(NONDipp )}]2 ([NONDipp ]2- =[O{SiMe2 NDipp}2 ]2- , Dipp=2,6-iPr2 C6 H3 ) activates ethene towards carbonylation with CO under mild conditions. An isolated bis-aluminacyclopropane compound reacted with CO via carbonylation of an Al-C bond, followed by an intramolecular hydrogen shift to form K2 [Al(NONDipp )(µ-CH2 CH=CO-1κ2 C1,3 -2κO)Al(NONDipp )Et]. Restricting the chemistry to a mono-aluminium system allowed isolation of [Al(NONDipp )(CH2 CH2 CO-κ2 C1,3 )]- , which undergoes thermal isomerisation to form the [Al(NONDipp )(CH2 CH=CHO-κ2 C,O)]- anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.

A general synthesis of azetidines by copper-catalysed photoinduced anti-Baldwin radical cyclization of ynamides.

A general anti-Baldwin radical 4-exo-dig cyclization from nitrogen-substituted alkynes is reported. Upon reaction with a heteroleptic copper complex in the presence of an amine and under visible light irradiation, a range of ynamides were shown to smoothly cyclize to the corresponding azetidines, useful building blocks in natural product synthesis and medicinal chemistry, with full control of the regioselectivity of the cyclization resulting from a unique and underrated radical 4-exo-dig pathway.

Experimental and Computational Studies on the Acetate-Assisted C-H Activation of N-Aryl Imidazolium Salts at Rhodium and Iridium: A Chloride Additive Changes the Selectivity of C-H Activation.

Combined experimental and computational mechanistic studies of the reactions of unsymmetrical, para-substituted N-aryl imidazolium salts, L2-R1,R2, at [MCl2Cp*]2 (M = Rh, Ir) in the presence of NaOAc are reported. These proceed via intermediate N-heterocyclic carbene complexes that then allow an internal competition between two differently substituted aryl rings toward C-H activation to be monitored. At 348 K in dichloroethane C-H activation of the aryl with the more electron-withdrawing substituents is generally favored. DFT calculations show similar barriers for proton transfer and dissociative HOAc/Cl- ligand substitution, with proton transfer favoring electron-donating substituents, and ligand substitution favoring electron-withdrawing substituents. Microkinetic simulations reproduce the experimental preference implying that the ligand substitution step dominates selectivity. For several substrates, notably L2-F,OMe and L2-F,H, running the C-H activation reactions at 298 K in the presence of added [Et4N]Cl reverses the selectivity. The greater availability of chloride in solution makes an alternative dissociative interchange ligand substitution mechanism accessible, leaving proton transfer as selectivity determining and so favoring electron-donating substituents. Our results highlight the potential importance of the ligand substitution step in the interpretation of substituent effects and demonstrate how a simple additive, [Et4N]Cl, can have a dramatic effect on selectivity by changing the mechanism of ligand substitution.