Triply Bonded Pancake π-Dimers Stabilized by Tetravalent Actinides.

Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of π-stacking can present challenges in the design of materials owing to their weak, nondirectional nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap is possible, resulting in covalent so-called "pancake" bonds. Two-electron, multicenter single pancake bonds are well known, whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by a 3-fold reduction of hexaazatrinaphthylene (HAN) and subsequent stacking of the [HAN]3- triradicals. Our analysis reveals a multicenter covalent triple pancake bond consisting of a σ-orbital and two equivalent π-orbitals. An electrostatic stabilizing role is established for the tetravalent thorium and uranium ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of triply bonded π-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials.

Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single-Molecule Magnets.

The potassium silole K2 [SiC4 -2,5-(SiMe3 )2 -3,4-Ph2 ] reacts with [M(η8 -COT)(THF)4 ][BPh4 ] (M=Er, Y; COT=cyclo-octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon-oxygen bond of THF. The structure of the major product, [(µ-η8 : η8 -COT)M(µ-L1 )K]∞ (1M ), consists of polymeric chains of sandwich complexes, where the spiro-bicyclic silapyran ligand [C4 H8 OSiC4 (SiMe3 )2 Ph2 ]2- (L1 ) coordinates to potassium via the oxygen. The minor product [(µ-η8 : η8 -COT)M(µ-L1 )K(THF)]2 (2M ) features coordination of the silapyran to the rare-earth metal. In forming 1M and 2M , silole insertion into THF only occurs in the presence of potassium and the rare-earth metal, highlighting the importance of bimetallic synergy. The lower nucleophilicity of germanium(II) leads to contrasting reactivity of the potassium germole K2 [GeC4 -2,5-(SiMe3 )2 -3,4-Me2 ] towards [M(η8 -COT)(THF)4 ][BPh4 ], with intact transfer of the germole occurring to give the coordination polymers [{η5 -GeC4 (SiMe3 )2 Me2 }M(η8 -COT)K]∞ (3M ). Despite the differences in reactivity induced by the group 14 heteroatom, the single-molecule magnet properties of 1Er , 2Er and 3Er are similar, with thermally activated relaxation occurring via the first-excited Kramers doublet, subject to effective energy barriers of 122, 80 and 91 cm-1 , respectively. Compound 1Er is also analysed by high-frequency dynamic magnetic susceptibility measurements up to 106  Hz.

Targeted Synthesis of End-On Dinitrogen-Bridged Lanthanide Metallocenes and Their Reactivity as Divalent Synthons.

High-yield syntheses of the lanthanide dinitrogen complexes [(Cp2tttM)2(µ-1,2-N2)] (1M, M = Gd, Tb, Dy; Cpttt = 1,2,4-C5tBu3H2), in which the [N2]2- ligands solely adopt the rare end-on or 1,2-bridging mode, are reported. The bulk of the tert-butyl substituents and the smaller radii of gadolinium, terbium, and dysprosium preclude formation of the side-on dinitrogen bonding mode on steric grounds. Elongation of the nitrogen-nitrogen bond relative to N2 is observed in 1M, and their Raman spectra show a major absorption consistent with N═N double bonds. Computational analysis of 1Gd identifies that the local symmetry of the metallocene units lifts the degeneracy of two 5dπ orbitals, leading to differing overlap with the π* orbitals of [N2]2-, a consequence of which is that the dinitrogen ligand occupies a singlet ground state. Magnetic measurements reveal antiferromagnetic exchange in 1M and single-molecule magnet (SMM) behavior in 1Dy. Ab initio calculations show that the magnetic easy axis in the ground doublets of 1Tb and 1Dy align with the {M-N═N-M} connectivity, in contrast to the usual scenario in dysprosium metallocene SMMs, where the axis passes through the cyclopentadienyl ligands. The [N2]2- ligands in 1M allow these compounds to be regarded as two-electron reducing agents, serving as synthons for divalent gadolinium, terbium, and dysprosium. Proof of principle for this concept is obtained in the reactions of 1M with 2,2'-bipyridyl (bipy) to give [Cp2tttM(κ2-bipy)] (2M, M = Gd, Tb, Dy), in which the lanthanide is ligated by a bipy radical anion, with strong metal-ligand direct exchange coupling.

Dynamic Magnetic Properties of Germole-ligated Lanthanide Sandwich Complexes.

The first germole-ligated single-molecule magnets are reported, with contrasting properties found for the near-linear sandwich complexes [(η8 -COT)Ln(η5 -CpGe ]- , where Ln=Dy (1Dy ) or Er (1Er ), COT is cyclo-octatetraenyl and CpGe is [GeC4 -2,5-(SiMe3 )2 -3,4-Me2 ]2- . Whereas 1Er has an energy barrier of 120(1) cm-1 in zero applied field and open hysteresis loops up to 10 K, the relaxation in 1Dy is characterized by quantum tunneling within the ground state.

Structural and Magnetization Dynamics of Borohydride-Bridged Rare-Earth Metallocenium Cations.

The structure and magnetic properties of the bimetallic borohydride-bridged dysprosocenium compound [{(η5-Cpttt)(η5-CpMe4t)Dy}2(µ:κ2:κ2-BH4)]+[B(C6F5)4]- ([3Dy][B(C6F5)4]) are reported along with the solution-phase dynamics of the isostructural yttrium and lutetium analogues (Cpttt is 1,2,4-tri(tert-butyl)cyclopentadienyl, CpMe4t is tetramethyl(tert-butyl)cyclopentadienyl). The synthesis of [3M][B(C6F5)4] was accomplished in the 2:1 stoichiometric reactions of [(η5-Cpttt)(η5-CpMe4t)Dy(BH4)] (2M) with [CPh3][B(C6F5)4], with the metallocenes 2M obtained from reactions of the half-sandwich complexes [(η5-Cpttt)M(BH4)2(THF)] (1M) (M = Y, Dy, Lu) with NaCpMe4t. Crystallographic studies show significant lengthening of the M···B distance on moving through the series 1M, 2M, and 3M, with essentially linear {M···B···M} bridges in 3M. Multinuclear NMR spectroscopy indicates restricted rotation of the Cpttt ligands in 3Y and 3Lu in solution. The single-molecule magnet (SMM) properties of [3M][B(C6F5)4] are characterized by Raman and Orbach processes, with an effective barrier of 533(18) cm-1 and relaxation via the second-excited Kramers doublet. Although quantum tunneling of the magnetization (QTM) was not observed for [3M][B(C6F5)4], it was, surprisingly, found in its magnetically dilute version, which has a very similar barrier of Ueff = 499(21) cm-1. Consistent with this observation, slightly wider openings of the magnetic hysteresis loop at 2 K are found for [3M][B(C6F5)4] but not for the diluted analogue. The dynamic magnetic properties of the dysprosium SMMs and the role of exchange interactions in 3Dy are interpreted with the aid of multireference ab initio calculations.

Syntheses and Characterization of Main Group, Transition Metal, Lanthanide, and Actinide Complexes of Bidentate Acylpyrazolone Ligands.

The synthesis of acylpyrazolone salts and their complexes of main group elements, transition metals, lanthanides, and actinides are described and characterized inter alia by means of single-crystal X-ray crystallography, NMR, and IR spectroscopies. The complexes consist of two, three, or four acylprazolone ligands bound to the metal atom, resulting in a structurally diverse set of coordination complexes with (distorted) octahedral, pentagonal-bipyramidal, or antiprismatic arrangements. Several complexes proved to be polymeric in the solid state including heterobimetallic sodium/lanthanide coordination polymers. A selection of the polymeric compounds was analyzed via TG/DTA measurements to establish their stability. The ligands, in turn, were readily synthesized in good yields from commercially available hydrazine hydrochloride salts. These findings demonstrate that acylpyrazolone ligands can form complexes with metals of varying ionic radii, highlighted by their utility in other areas such as analytical and metal organic framework chemistry.

Identification of Oxidation State +1 in a Molecular Uranium Complex.

The concept of oxidation state plays a fundamentally important role in defining the chemistry of the elements. In the f block of the periodic table, well-known oxidation states in compounds of the lanthanides include 0, +2, +3 and +4, and oxidation states for the actinides range from +7 to +2. Oxidation state +1 is conspicuous by its absence from the f-block elements. Here we show that the uranium(II) metallocene [U(η5-C5iPr5)2] and the uranium(III) metallocene [IU(η5-C5iPr5)2] can be reduced by potassium graphite in the presence of 2.2.2-cryptand to the uranium(I) metallocene [U(η5-C5iPr5)2]- (1) (C5iPr5 = pentaisopropylcyclopentadienyl) as the salt of [K(2.2.2-cryptand)]+. An X-ray crystallographic study revealed that 1 has a bent metallocene structure, and theoretical studies and magnetic measurements confirmed that the electronic ground state of uranium(I) adopts a 5f3(7s/6dz2)1(6dx2-y2/6dxy)1 configuration. The metal-ligand bonding in 1 consists of contributions from uranium 5f, 6d, and 7s orbitals, with the 6d orbitals engaging in weak but non-negligible covalent interactions. Identification of the oxidation state +1 for uranium expands the range of isolable oxidation states for the f-block elements and potentially signposts a synthetic route to this elusive species for other actinides and the lanthanides.

Thorium- and Uranium-Mediated C-H Activation of a Silyl-Substituted Cyclobutadienyl Ligand.

Cyclobutadienyl complexes of the f-elements are a relatively new yet poorly understood class of sandwich and half-sandwich organometallic compounds. We now describe cyclobutadienyl transfer reactions of the magnesium reagent [(η4-Cb'''')Mg(THF)3] (1), where Cb'''' is tetrakis(trimethylsilyl)cyclobutadienyl, toward thorium(IV) and uranium(IV) tetrachlorides. The 1:1 stoichiometric reactions between 1 and AnCl4 proceed with intact transfer of Cb'''' to give the half-sandwich complexes [(η4-Cb'''')AnCl(µ-Cl)3Mg(THF)3] (An = Th, 2; An = U, 3). Using a 2:1 reaction stoichiometry produces [Mg2Cl3(THF)6][(η4-Cb'''')An(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(Cl)] (An = Th, [Mg2Cl3(THF)6][4]; An = U [Mg2Cl3(THF)6][5]), in which one Cb'''' ligand has undergone cyclometalation of a trimethylsilyl group, resulting in the formation of an An-C σ-bond, protonation of the four-membered ring, and an η3-allylic interaction with the actinide. Complex solution-phase dynamics are observed with multinuclear nuclear magnetic resonance spectroscopy for both sandwich complexes. A computational analysis of the reaction mechanism leading to the formation of 4 and 5 indicates that the cyclobutadienyl ligands undergo C-H activation across the actinide center.

Discovery of a Dysprosium Metallocene Single-Molecule Magnet with Two High-Temperature Orbach Processes.

Magnetic bistability in single-molecule magnets (SMMs) is a potential basis for new types of nanoscale information storage material. The standard model for thermally activated relaxation of the magnetization in SMMs is based on the occurrence of a single Orbach process. Here, we show that incorporating a phosphorus atom into the framework of the dysprosium metallocene [(CpiPr5)Dy(CpPEt4)]+[B(C6F5)4]- (CpiPr5 is penta-isopropylcyclopentadienyl, CpPEt4 is tetraethylphospholyl) leads to the occurrence of two distinct high-temperature Orbach processes, with energy barriers of 1410(10) and 747(7) cm-1, respectively. These barriers provide experimental evidence for two different spin-phonon coupling regimes, which we explain with the aid of ab initio calculations. The strong and highly axial crystal field in this SMM also allows magnetic hysteresis to be observed up to 70 K, using a scan rate of 25 Oe s-1. In characterizing this SMM, we show that a conventional Debye model and consideration of rotational contributions to the spin-phonon interaction are insufficient to explain the observed phenomena.

Dominance of Cyclobutadienyl Over Cyclopentadienyl in the Crystal Field Splitting in Dysprosium Single-Molecule Magnets.

Replacing a monoanionic cyclopentadienyl (Cp) ligand in dysprosium single-molecule magnets (SMMs) with a dianionic cyclobutadienyl (Cb) ligand in the sandwich complexes [(η4 -Cb'''')Dy(η5 -C5 Me4 t Bu)(BH4 )]- (1), [(η4 -Cb'''')Dy(η8 -Pn† )K(THF)] (2) and [(η4 -Cb'''')Dy(η8 -Pn† )]- (3) leads to larger energy barriers to magnetization reversal (Cb''''=C4 (SiMe3 )4 , Pn† =1,4-di(tri-isopropylsilyl)pentalenyl). Short distances to the Cb'''' ligands and longer distances to the Cp ligands in 1-3 are consistent with the crystal field splitting being dominated by the former. Theoretical analysis shows that the magnetic axes in the ground Kramers doublets of 1-3 are oriented towards the Cb'''' ligands. The theoretical axiality parameter and the relative axiality parameter Z and Zrel are introduced to facilitate comparisons of the SMM performance of 1-3 with a benchmark SMM. Increases in Z and Zrel when Cb''' replaces Cp signposts a route to SMMs with properties that could surpass leading systems.

Main Group Chemistry at the Interface with Molecular Magnetism.

Innovative synthetic coordination and, increasingly, organometallic chemistry are at the heart of advances in molecular magnetism. Smart ligand design is essential for implementing controlled modifications to the electronic structure and magnetic properties of transition metal and f-element compounds, and many important recent developments use nontraditional ligands based on low-coordinate main group elements to drive the field forward. This review charts progress in molecular magnetism from the perspective of ligands in which the donor atoms range from low-coordinate 2p elements-particularly carbon but also boron and nitrogen-to the heavier p-block elements such as phosphorus, arsenic, antimony, and even bismuth. Emphasis is placed on the role played by novel main group ligands in addressing magnetic anisotropy of transition metal and f-element compounds, which underpins the development of single-molecule magnets (SMMs), a family of magnetic materials that can retain magnetization in the absence of a magnetic field below a blocking temperature. Nontraditional p-block donor atoms, with their relatively diffuse valence orbitals and more diverse bonding characteristics, also introduce scope for tuning the spin-orbit coupling properties and metal-ligand covalency in molecular magnets, which has implications in areas such as magnetic exchange coupling and spin crossover phenomena. The chemistry encompasses transition metals, lanthanides, and actinides and describes recently discovered molecular magnets that can be regarded, currently, as defining the state of the art. This review identifies that main group chemistry at the interface molecular magnetism is an area with huge potential to deliver new types of molecular magnets with previously unseen properties and applications.

Spin-Crossover Properties of an Iron(II) Coordination Nanohoop.

Addition of the bipyridyl-embedded cycloparaphenylene nanohoop bipy[9]CPP to [Fe{H2 B(pyz)2 }] (pyz=pyrazolyl) produces the distorted octahedral complex [Fe(bipy[9]CPP){H2 B(pyz)2 }2 ] (1). The molecular structure of 1 shows that the nanohoop ligand contains a non-planar bipy unit. Magnetic susceptibility measurements indicate spin-crossover (SCO) behaviour with a T1/2 of 130 K, lower than that of 160 K observed with the related compound [Fe(bipy){H2 B(pyz)2 }2 ] (2), which contains a conventional bipy ligand. A computational study of 1 and 2 reveals that the curvature of the nanohoop leads to the different SCO properties, suggesting that the SCO behaviour of iron(II) can be tuned by varying the size and diameter of the nanohoop.

Coupling of Nitric Oxide and Release of Nitrous Oxide from Rare-Earth-Dinitrosyliron Complexes.

Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]- (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(µ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.

Ethene Activation and Catalytic Hydrogenation by a Low-Valent Uranium Pentalene Complex.

The reaction of the uranium(III) complex [U(η8-Pn††)(η5-Cp*)] (1) (Pn†† = C8H4(1,4-SiiPr3)2, Cp* = C5Me5) with ethene at atmospheric pressure produces the ethene-bridged diuranium complex [{(η8-Pn††)(η5-Cp*)U}2(µ-η2:η2-C2H4)] (2). A computational analysis of 2 revealed that coordination of ethene to uranium reduces the carbon-carbon bond order from 2 to a value consistent with a single bond, with a concomitant change in the formal uranium oxidation state from +3 in 1 to +4 in 2. Furthermore, the uranium-ethene bonding in 2 is of the δ type, with the dominant uranium contribution being from f-d hybrid orbitals. Complex 2 reacts with hydrogen to produce ethane and reform 1, leading to the discovery that complex 1 also catalyzes the hydrogenation of ethene under ambient conditions.

Carbonyl Back-Bonding Influencing the Rate of Quantum Tunnelling in a Dysprosium Metallocene Single-Molecule Magnet.

The isocarbonyl-ligated metallocene coordination polymers [Cp*2M(µ-OC)W(Cp)(CO)(µ-CO)]∞ were synthesized with M = Gd (1, L = THF) and Dy (2, no L). In a zero direct-current field, the dysprosium version 2 was found to be a single-molecule magnet (SMM), with analysis of the dynamic magnetic susceptibility data revealing that the axial metallocene coordination environment leads to a large anisotropy barrier of 557(18) cm-1 and a fast quantum-tunnelling rate of ∼3.7 ms. Theoretical analysis of two truncated versions of 2, [Cp*2Dy{(µ-OC)W(Cp)(CO)2}2]- (2a), and [Cp*2Dy(OC)2]+ (2b), in which the effects of electron correlation outside the 4f orbital space were studied, revealed that tungsten-to-carbonyl back-donation plays an important role in determining the strength of the competing equatorial field at dysprosium and, hence, the dynamic magnetic properties. The finding that a classical organo-transition-metal bonding scenario can be used as an indirect way of tuning the rate of quantum tunnelling potentially provides an alternative chemical strategy for utilizing the fast magnetic relaxation properties of SMMs.

Isolation of a Perfectly Linear Uranium(II) Metallocene.

Reduction of the uranium(III) metallocene [(η5 -C5 i Pr5 )2 UI] (1) with potassium graphite produces the "second-generation" uranocene [(η5 -C5 i Pr5 )2 U] (2), which contains uranium in the formal divalent oxidation state. The geometry of 2 is that of a perfectly linear bis(cyclopentadienyl) sandwich complex, with the ground-state valence electron configuration of uranium(II) revealed by electronic spectroscopy and density functional theory to be 5f3 6d1 . Appreciable covalent contributions to the metal-ligand bonds were determined from a computational study of 2, including participation from the uranium 5f and 6d orbitals. Whereas three unpaired electrons in 2 occupy orbitals with essentially pure 5f character, the fourth electron resides in an orbital defined by strong 7s-6d z 2 mixing.

Cyclopentadienyl Ligands in Lanthanide Single-Molecule Magnets: One Ring To Rule Them All?

The discovery of materials capable of storing magnetic information at the level of single molecules and even single atoms has fueled renewed interest in the slow magnetic relaxation properties of single-molecule magnets (SMMs). The lanthanide elements, especially dysprosium, continue to play a pivotal role in the development of potential nanoscale applications of SMMs, including, for example, in molecular spintronics and quantum computing. Aside from their fundamentally fascinating physics, the realization of functional materials based on SMMs requires significant scientific and technical challenges to be overcome. In particular, extremely low temperatures are needed to observe slow magnetic relaxation, and while many SMMs possess a measurable energy barrier to reversal of the magnetization ( Ueff), very few such materials display the important properties of magnetic hysteresis with remanence and coercivity. Werner-type coordination chemistry has been the dominant method used in the synthesis of lanthanide SMMs, and most of our knowledge and understanding of these materials is built on the many important contributions based on this approach. In contrast, lanthanide organometallic chemistry and lanthanide magnetochemistry have effectively evolved along separate lines, hence our goal was to promote a new direction in single-molecule magnetism by uniting the nonclassical organometallic synthetic approach with the traditionally distinct field of molecular magnetism. Over the last several years, our work on SMMs has focused on obtaining a detailed understanding of why magnetic materials based on the dysprosium metallocene cation building block {Cp2Dy}+ display slow magnetic relaxation. Specifically, we aspired to control the SMM properties using novel coordination chemistry in a way that hinges on key considerations, such as the strength and the symmetry of the crystal field. In establishing that the two cyclopentadienyl ligands combine to provide a strongly axial crystal field, we were able to propose a robust magneto-structural correlation for understanding the properties of dysprosium metallocene SMMs. In doing so, a blueprint was established that allows Ueff and the magnetic blocking temperature ( TB) to be improved in a well-defined way. Although experimental discoveries with SMMs occur more rapidly than quantitative theory can (currently) process and explain, a clear message emanating from the literature is that a combination of the two approaches is most effective. In this Account, we summarize the main findings from our own work on dysprosium metallocene SMMs, and consider them in the light of related experimental studies and theoretical interpretations of related materials reported by other protagonists. In doing so, we aim to contribute to the nascent and healthy debate on the nature of spin dynamics in SMMs and allied molecular nanomagnets, which will be crucial for the further advancement of this vibrant research field.

Uranocenium: Synthesis, Structure, and Chemical Bonding.

Abstraction of iodide from [(η5 -C5 i Pr5 )2 UI] (1) produced the cationic uranium(III) metallocene [(η5 -C5 i Pr5 )2 U]+ (2) as a salt of [B(C6 F5 )4 ]- . The structure of 2 consists of unsymmetrically bonded cyclopentadienyl ligands and a bending angle of 167.82° at uranium. Analysis of the bonding in 2 showed that the uranium 5f orbitals are strongly split and mixed with the ligand orbitals, thus leading to non-negligible covalent contributions to the bonding. Investigation of the dynamic magnetic properties of 2 revealed that the 5f covalency leads to partially quenched anisotropy and fast magnetic relaxation in zero applied magnetic field. Application of a magnetic field leads to dominant relaxation by a Raman process.

Rare-Earth Cyclobutadienyl Sandwich Complexes: Synthesis, Structure and Dynamic Magnetic Properties.

The potassium cyclobutadienyl [K2 {η4 -C4 (SiMe3 )4 }] (1) reacts with MCl3 (THF)3.5 (M=Y, Dy) to give the first rare-earth cyclobutadienyl complexes, that is, the complex anions [M{η4 -C4 (SiMe3 )4 }{η4 -C4 (SiMe3 )3 -κ-(CH2 SiMe2 }]2- , (2M ), as their dipotassium salts. The tuck-in alkyl ligand in 2M is thought to form through deprotonation of the "squarocene" complexes [M{η4 -C4 (SiMe3 )4 }2 ]- by 1. Complex 2Dy is a single-molecule magnet, but with prominent quantum tunneling. An anisotropy barrier of 323(22) cm-1 was determined for 2Dy in an applied field of 1 kOe, and magnetic hysteresis loops were observed up to 7 K.

A Zinc Catalyzed C(sp3 )-C(sp2 ) Suzuki-Miyaura Cross-Coupling Reaction Mediated by Aryl-Zincates.

The Suzuki-Miyaura (SM) reaction is one of the most important methods for C-C bond formation in chemical synthesis. In this communication, we show for the first time that the low toxicity, inexpensive element zinc is able to catalyze SM reactions. The cross-coupling of benzyl bromides with aryl borates is catalyzed by ZnBr2 , in a process that is free from added ligand, and is compatible with a range of functionalized benzyl bromides and arylboronic acid pinacol esters. Initial mechanistic investigations indicate that the selective in situ formation of triaryl zincates is crucial to promote selective cross-coupling reactivity, which is facilitated by employing an arylborate of optimal nucleophilicity.