Azophosphines: Synthesis, Structure and Coordination Chemistry.

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus-containing analogues of triazenes are underexplored but offer great potential as flexible and small bite-angle ligands. This manuscript explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.

Mechanistic studies on single-electron transfer in frustrated Lewis pairs and its application to main-group chemistry.

Advances in the field of frustrated Lewis pair (FLP) chemistry have led to the discovery of radical pairs, obtained by a single-electron transfer (SET) from the Lewis base to the Lewis acid. Radical pairs are intriguing for their potential to enable cooperative activation of challenging substrates (e.g., CH4, N2) in a homolytic fashion, as well as the exploration of novel radical reactions. In this review, we will cover the two known mechanisms of SET in FLPs-thermal and photoinduced-along with methods (i.e., CV, DFT, UV-vis) to predict the mechanism and to characterise the involved electron donors and acceptors. Furthermore, the available techniques (i.e., EPR, UV-vis, transient absorption spectroscopy) for studying the corresponding radical pairs will be discussed. Initially, two model systems (PMes3/CPh3+ and PMes3/B(C6F5)3) will be reviewed to highlight the difference between a thermal and a photoinduced SET mechanism. Additionally, three cases are analysed to provide further tools and insights into characterizing electron donors and acceptors, and the associated radical pairs. Firstly, a thermal SET process between LiHMDS and [TEMPO][BF4] is discussed. Next, the influence of Lewis acid complexation on the electron acceptor will be highlighted to facilitate a SET between (pBrPh)3N and TCNQ. Finally, an analysis of sulfonium salts as electron acceptors will demonstrate how to manage systems with rapidly decomposing radical species. This framework equips the reader with an expanded array of tools for both predicting and characterizing SET events within FLP chemistry, thereby enabling its extension and application to the broader domain of main-group (photo)redox chemistry.

Homolytic C-H Bond Activation by Phosphine-Quinone-Based Radical Ion Pairs.

Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine-quinone systems and explore their potential for the activation of C-H bonds. PMes3 (Mes=2,4,6-Me3 C6 H2 ) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P-O bonded zwitterionic adduct Mes3 P-DDQ (1), while the reaction with the sterically more crowded PTip3 (Tip=2,4,6-iPr3 C6 H2 ) afforded C-H bond activation product Tip2 P(H)(2-[CMe2 (DDQ)]-4,6-iPr2 -C6 H2 ) (2). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip3 ]⋅+ [DDQ]⋅- , and subsequent homolytic C-H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip2 P(H)(2-[CMe2 {TCQ-B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (4, TCQ=tetrachloro-1,4-benzoquinone) and Tip2 P(H)(2-[CMe2 {oQtBu -B(C6 F5 )3 }]-4,6-iPr2 -C6 H2 ) (8, oQtBu =3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip3 with Lewis-acid activated quinones, TCQ-B(C6 F5 )3 and oQtBu -B(C6 F5 )3 , respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C-H bond activation by the synergistic action of radical ion pairs.

Simultaneous detection of pesticides and pharmaceuticals in three types of bio-based fertilizers by an improved QuEChERS method coupled with UHPLC-q-ToF-MS/MS.

Bio-based fertilizers (BBFs) have the potential to contain both pesticides and pharmaceutical residues, which may pose a threat to soils, crops, and human health. However, no analytical screening method is available currently to simultaneously analyze a wide range of contaminants in the complex origin-dependent matrices of BBFs. To fill this gap, our study tested and improved an original QuEChERS method (OQM) for simultaneously analyzing 78 pesticides and 18 pharmaceuticals in BBFs of animal, plant, and ashed sewage sludge origin. In spiked recovery experiments, 34-58 pharmaceuticals and pesticides were well recovered (recovery of 70-120%) via OQM at spiking concentrations levels of 10 ng/g and 50 ng/g in these three different types of BBFs. To improve the extraction efficiency further, ultrasonication and end-over-end rotation were added based on OQM, resulting in the improved QuEChERS method (IQM) that could recover 57-79 pesticides and pharmaceuticals, in the range of 70-120%. The detection limits of this method were of 0.16-4.32/0.48-12.97 ng/g, 0.03-11.02/0.10-33.06 ng/g, and 0.06-5.18/0.18-15.54 ng/g for animal, plant, and ash-based BBF, respectively. Finally, the IQM was employed to screen 15 BBF samples of various origins. 15 BBFs contained at least one pesticide or pharmaceutical with ibuprofen being frequently detected in at concentration levels of 4.1-181 ng/g. No compounds were detected in ash-based BBFs.

Insights into Single-Electron-Transfer Processes in Frustrated Lewis Pair Chemistry and Related Donor-Acceptor Systems in Main Group Chemistry.

The activation and utilization of substrates mediated by Frustrated Lewis Pairs (FLPs) was initially believed to occur solely via a two-electron, cooperative mechanism. More recently, the occurrence of a single-electron transfer (SET) from the Lewis base to the Lewis acid was observed, indicating that mechanisms that proceed via one-electron-transfer processes are also feasible. As such, SET in FLP systems leads to the formation of radical ion pairs, which have recently been more frequently observed. In this review, we aim to discuss the seminal findings regarding the recently established insights into the SET processes in FLP chemistry as well as highlight examples of this radical formation process. In addition, applications of reported main group radicals will also be reviewed and discussed in the context of the understanding of SET processes in FLP systems.

Safe and sustainable by design: A computer-based approach to redesign chemicals for reduced environmental hazards.

Persistency of chemicals in the environment is seen a pressing issue as it results in accumulation of chemicals over time. Persistent chemicals can be an asset in a well-functioning circular economy where products are more durable and can be reused or recycled. This objective can however not always be fulfilled as release of chemicals from products into the environment can be inherently coupled to their use. In these situations, chemicals should be designed for degradation. In this study, a systematic and computer-aided workflow was developed to facilitate the chemical redesign for reduced persistency. The approach includes elements of Essential Use, Alternatives Assessment and Green and Circular Chemistry and ties into goals recently formulated in the context of the EU Green Deal. The organophosphate chemical triisobutylphosphate (TiBP) was used as a case study for exploration of the approach, as its emission to the environment was expected to be inevitable when used as a flame retardant. Over 6.3 million alternative structures were created in silico and filtered based on QSAR outputs to remove potentially non-readily biodegradable structures. With a multi-criteria analysis based on predicted properties and synthesizability a top 500 of most desirable structures was identified. The target structure (di-n-butyl (2-hydroxyethyl) phosphate) was manually selected and synthesized. The approach can be expanded and further verified to reach its full potential in the mitigation of chemical pollution and to help enable a safe circular economy.

Atypical and Asymmetric 1,3-P,N Ligands: Synthesis, Coordination and Catalytic Performance of Cycloiminophosphanes.

Novel seven-membered cyclic imine-based 1,3-P,N ligands were obtained by capturing a Beckmann nitrilium ion intermediate generated in situ from cyclohexanone with benzotriazole, and then displacing it by a secondary phosphane under triflic acid promotion. These "cycloiminophosphanes" possess flexible non-isomerizable tetrahydroazepine rings with a high basicity; this sets them apart from previously reported iminophophanes. The donor strength of the ligands was investigated by using their P-κ1 - and P,N-κ2 -tungsten(0) carbonyl complexes, by determining the IR frequency of the trans-CO ligands. Complexes with [RhCp*Cl2 ]2 demonstrated the hemilability of the ligands, giving a dynamic equilibrium of κ1 and κ2 species; treatment with AgOTf gives full conversion to the κ2 complex. The potential for catalysis was shown in the RuII -catalyzed, solvent-free hydration of benzonitrile and the RuII - and IrI -catalyzed transfer hydrogenation of cyclohexanone in isopropanol. Finally, to enable access to asymmetric catalysts, chiral cycloiminophosphanes were prepared from l-menthone, as well as their P,N-κ2 -RhIII and a P-κ1 -RuII complexes.

Phosphorus recovery and recycling - closing the loop.

There is a clear and pressing need to better manage our planet's resources. Phosphorus is a crucial element for life, but the natural phosphorus cycle has been perturbed to such an extent that humanity faces two dovetailing problems: the dwindling supply of phosphate rock as a resource, and the overabundance of phosphate in water systems leading to eutrophication. This Tutorial Review will explore the current routes to industrial phosphorus compounds, and innovative academic routes towards accessing these same products in a more sustainable manner. It will then describe the many ways that useful phosphate can be recovered from waste streams, and how it can be recycled and used as a resource for new products. Finally, we will briefly discuss the barriers that have thus far prevented the widespread adoption of these technologies, and how we can close the loop to establish a modern phosphorus cycle.

Single-Electron Transfer in Frustrated Lewis Pair Chemistry.

Frustrated Lewis pairs (FLPs) are well known for their ability to activate small molecules. Recent reports of radical formation within such systems indicate single-electron transfer (SET) could play an important role in their chemistry. Herein, we investigate radical formation upon reacting FLP systems with dihydrogen, triphenyltin hydride, or tetrachloro-1,4-benzoquinone (TCQ) both experimentally and computationally to determine the nature of the single-electron transfer (SET) events; that is, being direct SET to B(C6 F5 )3 or not. The reactions of H2 and Ph3 SnH with archetypal P/B FLP systems do not proceed via a radical mechanism. In contrast, reaction with TCQ proceeds via SET, which is only feasible by Lewis acid coordination to the substrate. Furthermore, SET from the Lewis base to the Lewis acid-substrate adduct may be prevalent in other reported examples of radical FLP chemistry, which provides important design principles for radical main-group chemistry.

Easy Access to Phosphine-Borane Building Blocks.

In this paper, we highlight the synthesis of a variety of primary phosphine-boranes (RPH2 ⋅BH3 ) from the corresponding dichlorophosphines, simply by using Li[BH4 ] as reductant and provider of the BH3 protecting group. The method offers facile access not only to alkyl- and arylphosphine-boranes, but also to aminophosphine-boranes (R2 NPH2 ⋅BH3 ) that are convenient building blocks but without the protecting BH3 moiety thermally labile and notoriously difficult to handle. The borane-protected primary phosphines can be doubly deprotonated using n-butyllithium to provide soluble phosphanediides Li2 [RP⋅BH3 ] of which the phenyl-derivative Li2 [PhP⋅BH3 ] was structurally characterized in the solid state.

A Phosphinine-Derived 1-Phospha-7-Bora-Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds.

Invited for the cover of this issue are the groups of Ruth M. Gschwind and Robert Wolf (University of Regensburg), Christian Müller (Freie Universität Berlin), and J. Chris Slootweg (University of Amsterdam). The image depicts playing cards representing the reported reactions involving 1-phospha-7-bora-norbornadiene. Read the full text of the article at 10.1002/chem.202000266.

Novel brominated flame retardants - A review of their occurrence in indoor air, dust, consumer goods and food.

This critical review summarizes the occurrence of 63 novel brominated flame retardants (NBFRs) in indoor air, dust, consumer goods and food. It includes their EU registration and (potential) risks. The increasing application of NBFRs calls for more research on their occurrence, environmental fate and toxicity. This review reports which NBFRs are actually being studied, which are detected and which are of most concern. It also connects data from the European Chemical Association on NBFRs with other scientific information. Large knowledge gaps emerged for 28 (out of 63) NBFRs, which were not included in any monitoring programs or other studies. This also indicates the need for optimized analytical methods including all NBFRs. Further research on indoor environments, emission sources and potential leaching is also necessary. High concentrations of 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP), decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were often reported. The detection of hexabromobenzene (HBB), pentabromotoluene (PBT), 1,4-dimethyltetrabromobenzene (TBX), 4-(1,2-dibromoethyl)-1,2-dibromocyclohexane (DBE-DBCH) and tetrabromobisphenol A bis(2,3-dibromopropyl) ether (TBBPA-BDBPE) also raises concern.

Mixed Phosphatetrahedranes.

P-yramids: Tetrahedranes are highly strained molecules, and the all-carbon (CtBu)4 and all-phosphorus species P4 have been known for decades and centuries, respectively. Despite this, the mixed P/C tetrahedranes were unknown until recently when the syntheses of the phosphatetrahedranes P(CtBu)3 and P2 (CtBu)2 were reported by the research groups of Cummins and Wolf.

Photoinduced and Thermal Single-Electron Transfer to Generate Radicals from Frustrated Lewis Pairs.

Archetypal phosphine/borane frustrated Lewis pairs (FLPs) are famed for their ability to activate small molecules. The mechanism is generally believed to involve two-electron processes. However, the detection of radical intermediates indicates that single-electron transfer (SET) generating frustrated radical pairs could also play an important role. These highly reactive radical species typically have significantly higher energy than the FLP, which prompted this investigation into their formation. Herein, we provide evidence that the classical phosphine/borane combinations PMes3 /B(C6 F5 )3 and PtBu3 /B(C6 F5 )3 both form an electron donor-acceptor (charge-transfer) complex that undergoes visible-light-induced SET to form the corresponding highly reactive radical-ion pairs. Subsequently, we show that by tuning the properties of the Lewis acid/base pair, the energy required for SET can be reduced to become thermally accessible.

A Phosphinine-Derived 1-Phospha-7-Bora-Norbornadiene: Frustrated Lewis Pair Type Activation of Triple Bonds.

Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2. The C≡N triple bonds of nitriles insert into the P-B bond of 2 with concomitant C-B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4 -phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus-boron bond in 2, which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P-B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition.

New Insights in Frustrated Lewis Pair Chemistry with Azides.

The geminal frustrated Lewis pair (FLP) tBu2 PCH2 BPh2 (1) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes-N3 and tBu-N3 are used. The reaction of 1 with Me3 Si-N3 is believed to follow the same course, yet subsequent N2 elimination occurs to afford a four-membered heterocycle (5), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.

Pyridyl-Functionalized 1-Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di-π-Methane Rearrangement.

The [4+2] cycloaddition of 2-(2'-pyridyl)-4,6-diphenyl-λ3 -phosphinine with the highly reactive dienophile hexafluoro-2-butyne has been studied and the first pyridyl-functionalized 1-phosphabarrelene was obtained and structurally characterized. Although monodentate CF3 -1-phosphabarrelenes show only a poor coordination ability, the chelating nature of the novel P,N-hybrid ligand gives access to various transition-metal complexes. Upon irradiation with UV light, the pyridyl-functionalized 1-phosphabarrelene undergoes a rather selective di-π-methane rearrangement in the coordination sphere of the metal center, leading to the formation of a complex based on a hitherto unknown pyridyl-functionalized 5-phosphasemibullvalene derivative. DFT calculations provide first insights into the mechanism of this reaction.

Parallels between Metal-Ligand Cooperativity and Frustrated Lewis Pairs.

Metal ligand cooperativity (MLC) and frustrated Lewis pair (FLP) chemistry both feature the cooperative action of a Lewis acidic and a Lewis basic site on a substrate. A lot of work has been carried out in the field of FLPs to prevent Lewis adduct formation, which often reduces the FLP reactivity. Parallels are drawn between the two systems by looking at their reactivity with CO2, and we explore the role of steric bulk in preventing dimer formation in MLC systems.

Phosphinine-Based Ligands in Gold-Catalyzed Reactions.

A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur ) was calculated to get insight into the steric properties, [LNi(CO)3 ] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L-M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI -catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts.