Copper(I) Catalysed Diboron(4) Reduction of Nitrous Oxide.

A process for the catalytic reduction of nitrous oxide using NHC-ligated copper(I) tert-butoxide precatalysts and B2pin2 as the reductant is reported. The reaction proceeds under mild conditions via copper(I)-boryl intermediates which react with N2O by facile O-atom insertion into the Cu-B bond and liberate N2. Turnover numbers > 800 can be achieved at 80 °C under 1 bar N2O.

Synthetic and Mechanistic Studies into the Reductive Functionalization of Nitro Compounds Catalyzed by an Iron(salen) Complex.

We report on the use of a simple, bench-stable [Fe(salen)2]-µ-oxo precatalyst in the reduction of nitro compounds. The reaction proceeds at room temperature across a range of substrates, including nitro aromatics and aliphatics. By changing the reducing agent from pinacol borane (HBpin) to phenyl silane (H3SiPh), we can chemoselectively reduce nitro compounds while retaining carbonyl functionality. Our mechanistic studies, which include kinetics, electron paramagnetic resonance (EPR), mass spectrometry, and quantum chemistry, indicate the presence of a nitroso intermediate and the generation of an on-cycle iron hydride as a key catalytic intermediate. Based on this mechanistic insight, we were able to extend the chemistry to hydroamination and identified a simple substrate feature (alkene lowest unoccupied molecular orbital (LUMO) energy) that could be used to predict which alkenes would result in productive catalysis.

Capture of mechanically interlocked molecules by rhodium-mediated terminal alkyne dimerisation.

The transition metal-mediated dimerisation of terminal alkynes is an attractive and atom-economic method for preparing conjugated 1,3-enynes. Using a phosphine-based macrocyclic pincer ligand, we demonstrate how this transformation can be extended to the synthesis of novel, hydrocarbon-based interlocked molecules: a rotaxane by 'active' metal template synthesis and a catenane by sequential 'active' and 'passive' metal template procedures.

The Complex Reactivity of [(salen)Fe]2(µ-O) with HBpin and Its Implications in Catalysis.

We report a detailed study into the method of precatalyst activation during alkyne cyclotrimerization. During these studies we have prepared a homologous series of Fe(III)-µ-oxo(salen) complexes and use a range of techniques including UV-vis, reaction monitoring studies, single crystal X-ray diffraction, NMR spectroscopy, and LIFDI mass spectrometry to provide experimental evidence for the nature of the on-cycle iron catalyst. These data infer the likelihood of ligand reduction, generating an iron(salan)-boryl complex as a key on-cycle intermediate. We use DFT studies to interrogate spin states, connecting this to experimentally identified diamagnetic and paramagnetic species. The extreme conformational flexibility of the salan system appears connected to challenges associated with crystallization of likely on-cycle species.

Iridium complexes of an ortho-trifluoromethylphenyl substituted PONOP pincer ligand.

The synthesis and iridium coordination chemistry of a new pyridine-based phosphinito pincer ligand 2,6-(ArF2PO)2C5H3N (PONOP-ArF; ArF = 2-(CF3)C6H4) are described, where the P-donors have ortho-trifluoromethylphenyl substituents. The iridium(III) 2,2'-biphenyl (biph) derivative [Ir(PONOP-ArF)(biph)Cl] was obtained by reaction with [Ir(biph)(COD)Cl]2 (COD = 1,5-cyclooctadiene) and subsequent halide ion abstraction enabled isolation of [Ir(PONOP-ArF)(biph)]+ which features an Ir ← F-C bonding interaction in the solid state. Hydrogenolysis of the biphenyl ligand and formation of [Ir(PONOP-ArF)(H)2]+ was achieved by prolonged reaction of [Ir(PONOP-ArF)(biph)]+ with dihydrogen. This transformation paved the way for isolation and crystallographic characterisation of low valent iridium derivatives through treatment of the dihydride with tert-butylethylene (TBE). The iridium(I) π-complex [Ir(PONOP-ArF)(TBE)]+ is thermally stable but substitution of TBE can be achieved by reaction with carbon monoxide. The solid-state structure of the mono-carbonyl product [Ir(PONOP-ArF)(CO)]+ is notable for an intermolecular anagostic interaction between the metal centre and a pentane molecule which co-crystallises within a cleft defined by two aryl phosphine substituents.

Taming PH3: State of the Art and Future Directions in Synthesis.

Appetite for reactions involving PH3 has grown in the past few years. This in part is due to the ability to generate PH3 cleanly and safely via digestion of cheap metal phosphides with acids, thus avoiding pressurized cylinders and specialized equipment. In this perspective we highlight current trends in forming new P-C/P-OC bonds with PH3 and discuss the challenges involved with selectivity and product separation encumbering these reactions. We highlight the reactivity of PH3 with main group reagents, building on the early pioneering work with transition metal complexes and PH3. Additionally, we highlight the recent renewal of interest in alkali metal sources of H2P- which are proving to be useful synthons for chemistry across the periodic table. Such MPH2 sources are being used to generate the desired products in a more controlled fashion and are allowing access to unexplored phosphorus-containing species.

Broken Promises? On the Continued Challenges Faced in Catalytic Hydrophosphination.

In this Perspective, we discuss what we perceive to be the continued challenges faced in catalytic hydrophosphination chemistry. Currently the literature is dominated by catalysts, many of which are highly effective, that generate the same phosphorus architectures, e.g., anti-Markovnikov products from the reaction of activated alkenes and alkynes with diarylphosphines. We highlight the state of the art in stereoselective hydrophosphination and the scope and limitations of chemoselective hydrophosphination with primary phosphines and PH3. We also highlight the progress in the chemistry of the heavier homologues. In general, we have tried to emphasize what is missing from our hydrophosphination armament, with the aim of guiding future research targets.

Synthesis and reactivity of iridium complexes of a macrocyclic PNP pincer ligand.

Having recently reported on the synthesis and rhodium complexes of the novel macrocyclic pincer ligand PNP-14, which is derived from lutidine and features terminal phosphine donors trans-substituted with a tetradecamethylene linker (Dalton Trans., 2020, 49, 2077-2086 and Dalton Trans., 2020, 49, 16649-16652), we herein describe our findings critically examining the chemistry of iridium homologues. The five-coordinate iridium(i) and iridium(iii) complexes [Ir(PNP-14)(η2:η2-cyclooctadiene)][BArF4] and [Ir(PNP-14)(2,2'-biphenyl)][BArF4] are readily prepared and shown to be effective precursors for the generation of iridium(iii) dihydride dihydrogen, iridium(i) bis(ethylene), and iridium(i) carbonyl derivatives that highlight important periodic trends by comparison to rhodium counterparts. Reaction of [Ir(PNP-14)H2(H2)][BArF4] with 3,3-dimethylbutene induced triple C-H bond activation of the methylene chain, yielding an iridium(iii) allyl hydride derivative [Ir(PNP-14*)H][BArF4], whilst catalytic homocoupling of 3,3-dimethylbutyne into Z-tBuC[triple bond, length as m-dash]CCHCHtBu could be promoted at RT by [Ir(PNP-14)(η2:η2-cyclooctadiene)][BArF4] (TOFinitial = 28 h-1). The mechanism of the latter is proposed to involve formation and direct reaction of a vinylidene derivative with HC[triple bond, length as m-dash]CtBu outside of the macrocyclic ring and this suggestion is supported experimentally by isolation and crystallographic characterisation of a catalyst deactivation product.

Reactions of Rh(PNP) pincer complexes with terminal alkynes: homocoupling through a ring or not at all.

Through use of a bespoke macrocyclic variant, we demonstrate a novel approach for tuning the reactivity of rhodium PNP pincer complexes that enables formation of conjugated enynes from terminal alkynes, rather than vinylidene derivates. This concept is illustrated using tert-butylacetylene as the substrate and rationalised by a ring-induced switch in mechanism.

Synthesis and rhodium complexes of macrocyclic PNP and PONOP pincer ligands.

The synthesis of macrocyclic variants of commonly employed phosphine-based pincer ligands derived from lutidine (PNP-14) and 2,6-dihydroxypyridine (PONOP-14) is described, where the P-donors are trans-substituted with a tetradecamethylene linker. This was accomplished using an eight-step procedure involving borane protection, ring-closing olefin metathesis, chromatographic separation from the cis-substituted diastereomers, and borane deprotection. The rhodium coordination chemistry of these ligands has been explored, aided by the facile synthesis of 2,2'-biphenyl (biph) adducts [Rh(PNP-14)(biph)][BArF4] and [Rh(PONOP-14)(biph)][BArF4] (ArF = 3,5-(CF3)2C6H3). Subsequent hydrogenolysis enabled generation of dihydrogen, ethylene and carbonyl derivatives; notably the ν(CO) bands of the carbonyl complexes provide a means to compare the donor properties of the new pincer ligands with established acyclic congeners.

Synthesis and Structural Dynamics of Five-Coordinate Rh(III) and Ir(III) PNP and PONOP Pincer Complexes.

The synthesis and characterization of a homologous series of five-coordinate rhodium(III) and iridium(III) complexes of PNP (2,6-( tBu2PCH2)2C5H3N) and PONOP (2,6-( tBu2PO)2C5H3N) pincer ligands are described: [M(PNP)(biph)][BArF4] (M = Rh, 1a; Ir, 1b; biph = 2,2'-biphenyl; ArF = 3,5-(CF3)2C6H3) and [M(PONOP)(biph)][BArF4] (M = Rh, 2a; Ir, 2b). These complexes are structurally dynamic in solution, exhibiting pseudorotation of the biph ligand on the 1H NMR time scale (Δ G⧧ ca. 60 kJ mol-1) and, in the case of the flexible PNP complexes, undergoing interconversion between helical and puckered pincer ligand conformations (Δ G⧧ ca. 10 kJ mol-1). Remarkably, the latter is sufficiently facile that it persists in the solid state, leading to temperature-dependent disorder in the associated X-ray crystal structures. Reaction of 1 and 2 with CO occurs for the iridium congeners 1b and 2b, leading to the formation of sterically congested carbonyl derivatives.

A convenient method for the generation of {Rh(PNP)}+ and {Rh(PONOP)}+ fragments: reversible formation of vinylidene derivatives.

The substitution reactions of [Rh(COD)2][BArF4] with PNP and PONOP pincer ligands 2,6-bis(di-tert-butylphosphinomethyl)pyridine and 2,6-bis(di-tert-butylphosphinito)pyridine in the weakly coordinating solvent 1,2-F2C6H4 are shown to be an operationally simple method for the generation of reactive formally 14 VE rhodium(i) adducts in solution. Application of this methodology enables synthesis of known adducts of CO, N2, H2, previously unknown water complexes, and novel vinylidene derivatives [Rh(pincer)(CCHR)][BArF4] (R = tBu, 3,5-tBu2C6H3), through reversible reactions with terminal alkynes.