A Multiconfigurational Wave Function Theoretical Study on Electronic Structure and Magnetic Susceptibility of Dilanthanide Single Molecule Magnet.

Single molecule magnets (SMMs) have been a promising material for next-generation high-density information storage and molecular spintronics. N23--bridged dilanthanide complexes, {[(Me3Si)2N]2Ln(THF)(µ-η2:η2-N2)(THF)Ln[(Me3Si)2N]2}1-, exhibit high blocking temperatures and have been one of the promising candidates for future application. Rational understanding should be established between the magnetic properties and electronic structure. However, the theoretical study is still challenging due to the complexities in their electronic structures. Here, we theoretically studied the magnetic susceptibility of dilanthanide SMMs based on the state-of-the-art multistate-complete active space self-consistent field and perturbation theory at the second order and restricted active space state interaction with spin-orbit coupling calculations. Temperature dependence of the magnetic susceptibility (χmT-T curve) was quantitatively reproduced by the theoretical calculations. The complexities in the electronic states of these dilanthanide complexes originate from significantly strong static electron correlations in the lanthanide 4f and N2 π* orbitals and the SOC effect. The temperature dependence of the magnetic susceptibility results from the energy levels and magnetic properties of the low-lying excited state. The χmT values below 50 K are dominated by the ground state, while thermal distribution in the low-lying excited state affects the χmT values over 50 K. Saturation magnetization at low temperatures was also evaluated, and the result agrees with the experimental observation.

Carbon dioxide adsorption to UiO-66: theoretical analysis of binding energy and NMR properties.

UiO-66 is one of the most valuable metal-organic frameworks because of its excellent adsorption capability for gas molecules and its high stability towards water. Herein we investigated adsorption of carbon dioxide (CO2), acetone, and methanol to infinite UiO-66 using DFT calculations on an infinite system under periodic-boundary conditions and post-Hartree-Fock (SCS-MP2 and MP2.5) calculations on cluster models. Three to four molecules are adsorbed at each of four µ-OH groups bridging three Zr atoms in one unit cell (named Site I). Six molecules are adsorbed around three pillar ligands, where the molecule is loosely surrounded by three terephthalate ligands (named Site II). Also, six molecules are adsorbed around the pillar ligand in a different manner from that at Site II, where the molecule is surrounded by three terephthalate ligands (named Site III). Totally fifteen to sixteen CO2 molecules are adsorbed into one unit cell of UiO-66. The binding energy (BE) decreases in the order Site I > Site III > Site II for all three molecules studied here and in the order acetone > methanol ≫ CO2 in the three adsorption sites. At the site I, the protonic H atom of the µ-OH group interacts strongly with the negatively charged O atom of CO2, acetone and methanol, which is the origin of the largest BE value at this site. Although the DFT calculations present these decreasing orders of BE values correctly, the correction by post-Hartree-Fock calculations is not negligibly small and must be added for obtaining better BE values. We explored NMR spectra of UiO-66 with adsorbed CO2 molecules and found that the isotropic shielding constants of the 1H atom significantly differ among no CO2, one CO2 (at Sites I, II, or III), and fifteen CO2 adsorption cases (Sites I to III) but the isotropic 17O and 13C shielding constants change moderately by adsorption of fifteen CO2 molecules. Thus, 1H NMR measurement is a useful experiment for investigating CO2 adsorption.

Palladium cluster complex [Pd13(µ4-C7H7)6]2+ (C7H7 = tropylium) with an fcc-close-packed cuboctahedral Pd13 core and isomers: theoretical insight into ligand-control of the Pd13 core structure.

One of the challenging targets in today's chemistry is size-, shape- and metal-atom packing-controlled synthesis of nano-scale transition metal cluster complexes because key factors governing these features have been elusive. Here, we present a DFT study on a recently synthesized palladium cluster complex [Pd13(µ4-C7H7)6]2+ (named Cubo-µ4; C7H7 = tropylium) with an fcc-close-packed cuboctahedral Pd13 core and possible isomers. The stability decreases in the order Cubo-µ4 > [Pd13(µ3-C7H7)3(µ4-C7H7)3]2+ with an hcp-close-packed anticuboctahedral Pd13 core (Anti-µ3,4) > [Pd13(µ3-C7H7)6]2+ with a non-close packed icosahedral Pd13 core (Ih-µ3) > [Pd13(µ4-C7H7)6]2+ with an anticuboctahedral Pd13 core (Anti-µ4) > [Pd13(µ3-C7H7)6]2+ with a cuboctahedral Pd13 core (Cubo-µ3). This ordering disagrees with the stability of the Pd13 core. The key factor governing the stability and metal-atom packing manner of these Pd13 cluster complexes is not the stability of the Pd13 core but the interaction energy between the Pd13 core and the [(C7H7)6]2+ ligand shell. The interaction energy is mainly determined by the charge-transfer from the Pd13 core to the [(C7H7)6]2+ ligand shell and the coordination mode of the C7H7 ligand (µ3- vs. µ4-coordination bond). In the µ4-coordination, all seven C atoms of the C7H7 ligand interact with four Pd atoms of the Pd4 plane using two CC double bonds and one π-allyl moiety. On the other hand, in the µ3-coordination, one or two C atoms of C7H7 cannot form bonding interaction with the Pd atom of the Pd3 plane. Thus, the use of appropriate capping ligands is one of the key points in the synthesis of nano-scale metal cluster complexes.

Soft corrugated channel with synergistic exclusive discrimination gating for CO2 recognition in gas mixture.

Developing artificial porous systems with high molecular recognition performance is critical but very challenging to achieve selective uptake of a particular component from a mixture of many similar species, regardless of the size and affinity of these competing species. A porous platform that integrates multiple recognition mechanisms working cooperatively for highly efficient guest identification is desired. Here, we designed a flexible porous coordination polymer (PCP) and realised a corrugated channel system that cooperatively responds to only target gas molecules by taking advantage of its stereochemical shape, location of binding sites, and structural softness. The binding sites and structural deformation act synergistically, exhibiting exclusive discrimination gating (EDG) effect for selective gate-opening adsorption of CO2 over nine similar gas molecules, including N2, CH4, CO, O2, H2, Ar, C2H6, and even higher-affinity gases such as C2H2 and C2H4. Combining in-situ crystallographic experiments with theoretical studies, it is clear that this unparalleled ability to decipher the CO2 molecule is achieved through the coordination of framework dynamics, guest diffusion, and interaction energetics. Furthermore, the gas co-adsorption and breakthrough separation performance render the obtained PCP an efficient adsorbent for CO2 capture from various gas mixtures.

Isolation and Structures of Polyarene Palladium Nanoclusters.

We report that surrounding coordination of neutral six-membered arene rings affords molecularly well-defined organotransition metal nanoclusters. With the use of [2.2]paracyclophane as the face-capping arene ligand, we have isolated two polyarene palladium nanoclusters, one consisting of a hexakis-arene ligand shell and a hexagonal close-packed Pd13 anticuboctahedron trichloride core, and the other consisting of an octakis-arene ligand shell and a non-close-packed Pd17 square gyrobicupola dichloride core, both with Pd-Pd direct bonding. The µ4-facial coordination mode of arene was discovered through the structural characterization of the Pd13 cluster. Their Pd13 and Pd17 cores, which are distinct from the previously identified face-centered-cubic Pd13 core surrounded by seven-membered cycloheptatrienyl, are explained by stereochemical and theoretical analyses.

An Iridium/Aluminum Cooperative Strategy for the ß-C(sp3 )-H Borylation of Saturated Cyclic Amines.

Despite the widespread success in the functionalization of C(sp2 )-H bonds, the deliberate functionalization of C(sp3 )-H bonds in a highly site- and stereoselective manner remains a longstanding challenge. Herein, we report an iridium/aluminum cooperative catalytic system that enables the ß-selective C-H borylation of saturated cyclic amines and lactams. Furthermore, we have accomplished an enantioselective variant using binaphthol-derived chiral aluminum catalysts to forge C-B bonds with high levels of stereocontrol. Computational studies suggest that the formation of a Lewis pair with the substrates is crucial to lower the energy of the transition state for the rate-determining reductive elimination step.

Theoretical Study on the Vapochromic Ni(II)-Quinonoid Complex: One-Dimensional Stacking Structure-Based Color Switching.

Vapochromic crystals of Ni(II)-quinonoid complexes were theoretically investigated using density functional theory (DFT) calculations. Kato et al. previously reported that the purple crystals of a four-coordinate Ni(II)-quinonoid complex (1P) exhibited vapochromic characteristics upon exposure to methanol gas, resulting in orange crystals of the six-coordinate methanol-bound complex (1O) [Angew. Chem., Int. Ed.2017, 56, 2345-2349]. However, the authors did not characterize the crystal structure of 1P. In the present study, we computationally predicted the crystal structure of 1P by performing a crystal structure search with classical force-field computations followed by optimization using DFT calculations. The simulated powder X-ray diffraction pattern of the DFT-optimized structure agreed with experimental observations, indicating that our predicted crystal structure is reliable. Investigation of the optimized crystal structure of 1P revealed that its color change arose from changes in its 1D-band structure, which consists of Ni 3d orbitals and quinonoid π-orbitals. Intermolecular interactions were weakened upon the binding of methanol to the Ni(II) center in 1O. Consequently, the intermolecular 3d-π interaction in 1P lowered the band gap and induced the red-shifting of the monomeric four-coordinate Ni(II)-quinonoid complex. Meanwhile, the obtained absorption spectrum of 1O closely corresponded to that of the monomeric six-coordinate Ni(II)-quinonoid complex. Our study provides a new strategy for accurately predicting molecular crystal structures and reveals a new insight into vapochromism based on band structure color switching.

Theoretical Study of N-H σ-Bond Activation by Nickel(0) Complex: Reaction Mechanism, Electronic Processes, and Prediction of Better Ligand.

N-H σ-bond activation of alkylamine by Ni(PCy3) was investigated using density functional theory (DFT) calculations. When simple alkylamine NHMe2 is a reactant, both concerted oxidative addition in Ni(PCy3)(NHMe2) and ligand-to-ligand H transfer reaction in Ni(PCy3)(C2H4)(NHMe2) are endergonic and need a high activation energy. When NH(Me)(Bs) (Bs = SO2Ph, a model of tosyl group used in experiments) is a reactant, both reactions are exergonic and occur easily with a much smaller activation energy. The much larger reactivity of NH(Me)(Bs) than that of NHMe2 results from the stronger Ni-N(Me)(Bs) bond than the Ni-NMe2 bond and the presence of the Ni-O bonding interaction between the Bs group and the Ni atom in the product. N-Heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr), is computationally predicted to be better than PCy3 because the Ni-NMe2 and Ni-N(Me)(Bs) bonds in the IPr complex are stronger, respectively, than those of the PCy3 complex. The introduction of the electron-withdrawing Bs group to the N atom of amine and the use of IPr as a ligand are recommended for the N-H σ-bond activation. The C-H σ-bond activations of benzene via the oxidative addition and the ligand-to-ligand H transfer reaction were also investigated here for comparison with the N-H σ-bond activation. The differences between the C-H σ-bond activation of benzene and the N-H σ-bond activation of these amines are discussed in terms of the N-H, C-H, Ni-Ph, and Ni-NMe2, and Ni-N(Me)(Bs) bond energies and back-donation to benzene from the Ni atom.

Tunable acetylene sorption by flexible catenated metal-organic frameworks.

The safe storage of flammable gases, such as acetylene, is essential for current industrial purposes. However, the narrow pressure (P) and temperature range required for the industrial use of pure acetylene (100 < P < 200 kPa at 298 K) and its explosive behaviour at higher pressures make its storage and release challenging. Flexible metal-organic frameworks that exhibit a gated adsorption/desorption behaviour-in which guest uptake and release occur above threshold pressures, usually accompanied by framework deformations-have shown promise as storage adsorbents. Herein, the pressures for gas uptake and release of a series of zinc-based mixed-ligand catenated metal-organic frameworks were controlled by decorating its ligands with two different functional groups and changing their ratio. This affects the deformation energy of the framework, which in turn controls the gated behaviour. The materials offer good performances for acetylene storage with a usable capacity of ~90 v/v (77% of the overall amount) at 298 K and under a practical pressure range (100-150 kPa).

Single atom alloys vs. phase separated alloys in Cu, Ag, and Au atoms with Ni(111) and Ni, Pd, and Pt atoms with Cu(111): a theoretical exploration.

A single-atom alloy (SAA) consisting of an abundant metal host and a precious metal guest is a promising catalyst to reduce the cost without a loss of activity. DFT calculations of Ni- and Cu-based alloys nX/M(111) (X = Cu, Ag, or Au for M = Ni; X = Ni, Pd, or Pt for M = Cu; n = 1-4) reveal that a phase-separated alloy (PSA) is produced by Cu atoms with Ni(111) but an SAA is produced by Au atoms with Ni(111) and Pd and Pt atoms with Cu(111). In the Ni(111)-based Ag alloy and Cu(111)-based Ni alloy, the relative stabilities of the SAA and PSA depend on coverages of Ag on Ni(111) and Ni on Cu(111). The interaction energy (Eint) between the Xn cluster and M(111) host is larger than that between one X atom and the M(111) host, because the Xn cluster forms more bonding interactions with the M(111) host than does one X atom. When going from one X atom to the X4 cluster, the Eint values of Au and Pt clusters respectively with Ni(111) and Cu(111) increase to a lesser extent than those of Cu and Ni clusters respectively with Ni(111) and Cu(111). Consequently, Au and Pt atoms tend to form SAAs respectively with Ni(111) and Cu(111) hosts compared to Cu and Ni atoms. This trend in the Eint value is determined by the valence orbital energies of the X atom and the Xn cluster. Cu atoms in nCu/Ni(111) have a slightly positive charge but Ag atoms in nAg/Ni(111), Au atoms in nAu/Ni(111), and Ni, Pd, and Pt atoms in nX/Cu(111) (X = Ni, Pd, or Pt) have a negative charge. The negative charge increases in the order Ag < Au in nX/Ni(111) and Ni < Pd < Pt in nX/Cu(111). The Fermi level decreases in energy in the order nCu/Ni(111) ≥ Ni(111) > nAg/Ni(111) > nAu/Ni(111) and Cu(111) ≥ nNi/Cu(111) > nPd/Cu(111) > nPt/Cu(111). The d valence band center decreases in energy in almost the same order. The CO adsorption energy decreases in the order Ni(111) ∼ nCu/Ni(111) > nAg/Ni(111) ∼ nAu/Ni(111) and Cu(111) > nNi/Cu(111) > nPd/Cu(111) > nPt/Cu(111). These properties are explained based on the electronic structures.

Heterometallic d8 -d10 Coupling of Rh(I) and M(0) (M=Pd, Pt) in a Sandwich Framework of π-Conjugated Ligands.

A heterometallic M-M' bond formation is a key to construct atomically precise bimetallic clusters and materials. However, it is sometimes not straightforward to construct a heterometallic M-M' bond through conventional methods including redox condensation. Here, we found that a sandwich framework of π-conjugated unsaturated hydrocarbon ligands provides a unique coordination environment that facilitates unusual coupling of d8 RhI and d10 M0 (M=Pd, Pt). The molecular orbital analysis showed that the electron-accepting ability of the sandwich framework through back-donation allows the formation of a dσ-type Rh-Pd bond in a (d-d)18 electron system.

Theoretical Study of NO Dissociative Adsorption onto 3d Metal Particles M55 (M = Fe, Co, Ni, and Cu): Relation between the Reactivity and Position of the Metal Element in the Periodic Table.

NO dissociative adsorption onto 3d metal particles M55 (M = Fe, Co, Ni, and Cu) was investigated theoretically using density functional theory computations. A transition state exists at higher energy in the Cu case but at lower energy in the Fe, Co, and Ni cases than the reactant (sum of M55 and NO), indicating that Cu55 is not reactive for NO dissociative adsorption because NO desorption occurs more easily than the N-O bond cleavage in this case, but Fe55, Co55, and Ni55 are reactive because NO desorption needs a larger destabilization energy than the N-O bond cleavage. This result agrees with the experimental findings. The energy of transition state E(TS) becomes higher in the order of Fe < Co < Ni ≪ Cu. Exothermicity E exo (relative energy to the reactant) decreases in the order of Fe > Co > Ni ≫ Cu. These results indicate that the reactivity for NO dissociative adsorption decreases kinetically and thermodynamically in this order. In addition, the E(TS) and E exo values show that 3d metal particles are more reactive than 4d metal particles when a comparison is made in the same group of the periodic table. Charge transfer (CT) from the metal particle to NO increases as the reaction proceeds. The CT quantity to NO at the TS increases in the order of Cu < Ni < Co < Fe, identical to the increasing order of reactivity. The negative charges of the N and O atoms of the product (N and O adsorbed M55) increase in the order of Ni < Co < Cu < Fe, identical to the increasing order of E exo except for the Cu case; in the Cu case, the discrepancy between the order of E exo and those of the N and O negative charges arises from the presence of valence 4s electron of Cu because it suppresses the CT from N and O to Cu55. From these results, one can infer that the d-valence band-top energy of M55 plays an important role in determining the reactivity for NO dissociative adsorption. Truly, the d valence orbital energy decreases in the order of Fe > Co > Ni ≫ Cu and the 3d metal > 4d metal in the same group of the periodic table, which reflects the dependence of reactivity on the metal element position in the periodic table.

Host-Guest Interaction Modulation in Porous Coordination Polymers for Inverse Selective CO2 /C2 H2 Separation.

Controlling gas sorption by simple pore modification is important in molecular recognition and industrial separation processes. In particular, it is challenging to realize the inverse selectivity, which reduces the adsorption of a high-affinity gas and increases the adsorption of a low-affinity gas. Herein, an "opposite action" strategy is demonstrated for boosting CO2 /C2 H2 selectivity in porous coordination polymers (PCPs). A precise steric design of channel pores using an amino group as an additional interacting site enabled the synergetic increase in CO2 adsorption while suppressing the C2 H2 adsorption. Based on this strategy, two new ultramicroporous PCP physisorbents that are isostructural were synthesised. They exhibited the highest CO2 uptake and CO2 /C2 H2 volume uptake ratio at 298 K. Origin of this specific selectivity was verified by detailed density functional theory calculations. The breakthrough separation performances with remarkable stability and recyclability of both the PCPs render them relevant materials for C2 H2 purification from CO2 /C2 H2 mixtures.

Four-Electron Reduction of Dioxygen on a Metal Surface: Models of Dissociative and Associative Mechanisms in a Homogeneous System.

Two different four-electron reductions of dioxygen (O2) on a metal surface are reproduced in homogeneous systems. The reaction of the highly unsaturated (56-electron) tetraruthenium tetrahydride complex 1 with O2 readily afforded the bis(µ3-oxo) complex 3 via a dissociative mechanism that includes large electronic and geometric changes, i.e., a four-electron oxidation of the metal centers and an increase of 8 in the number of valence electrons. In contrast, the tetraruthenium hexahydride complex 2 induces a smooth H-atom transfer to the incorporated O2 species, and the O-OH bond is cleaved to afford the mono(µ3-oxo) complex 4 via an associative mechanism. Density functional theory calculations suggest that the higher degree of unsaturation in the tetrahydride system induces a significant interaction between the tetraruthenium core and the O2 moiety, enabling the large changes required for the dissociative mechanism.

Deacylative Carbon-Carbon Bond Cleavage of Ketone Equivalents: Applications to Radical Carbon-Carbon Bond Formation Reactions.

This article describes the synthetic application of ketone-derived oxaziridines as alkyl radical precursors in copper-catalyzed Carbon-Carbon bond formation reactions. Experimental and computational studies indicate a free radical mechanism, where alkyl radicals are efficiently generated via cleavage of a Carbon-Carbon bond of oxaziridines. Acyclic and unstrained cyclic oxaziridines are applicable to the present radical process, allowing for the generation of various alkyl radicals with good functional group compatibility.

Coordination Flexibility of the Rh(PXP) Complex to NH3, CO, and C2H4 (PXP = Diphosphine-Based Pincer Ligand; X = B, Al, and Ga): Theoretical Insight.

The recently synthesized rhodium-aluminum bimetallic complex Rh(PAlP) 1 (PAlP = pincer-type diphosphino-aluminyl ligand Al{[N(C6H4)]2NMe}[CH2P(iPr)2]2) containing a unique Rh-Al direct bond exhibits coordination flexibility because Rh and Al can play the role of coordination site for the substrate. DFT calculations of NH3, CO, and C2H4 adducts with 1 show that the Rh atom is favorable for all these substrate but the Al atom is as favorable as the Rh atom for NH3 and unfavorable for CO and C2H4. NH3 and CO prefer the coordination at the Rh-axial (Ax) site to the Rh-equatorial (Eq) site, but C2H4 prefers coordination at the Rh-Eq site to the Rh-Ax site. Consequently, two CO and C2H4 molecules coordinate with 1 at the Rh-Ax and Rh-Eq sites to afford trigonal bipyramidal complexes Rh(PAlP)(CO)2 and Rh(PAlP)(C2H4)2, which is consistent with the experimental observation of Rh(PAlP)(CO)2. Energy decomposition analysis reveals that an electrostatic term plays an important role for NH3 coordination with the Al atom of 1, because Al has a significantly large positive charge and NH3 has a much negatively charged N atom and exhibits a considerably negative electrostatic potential at the Al position. In B and Ga analogues Rh(PBP) 2 and Rh(PGaP) 3, B and Ga atoms are not good for CO and C2H4 like the Al atom in 1. NH3 adducts with 2 and 3 at the B and Ga sites are less stable than those adducts at the Rh-Ax site unlike the NH3 adduct with 1 at the Al site. This difference in the NH3 adduct between Rh(PAlP) and others (Rh(PBP) and Rh(PGaP)) arises from much less positive charges of B and Ga and a smaller atomic size of B than that of Al. These results indicate that the significantly large electropositive nature and appropriate atomic size of Al are responsible for the characteristic coordination flexibility of Rh(PAlP).

Methane Borylation Catalyzed by Ru, Rh, and Ir Complexes in Comparison with Cyclohexane Borylation: Theoretical Understanding and Prediction.

Methane borylation catalyzed by Cp*M(Bpin)n (M = Ru or Rh; HBpin = pinacolborane; n = 2 or 3) and (TMPhen)Ir(Bpin)3 (TMPhen = 3,4,7,8-tetramethyl-1,10-phenanthroline) was investigated by DFT in comparison with cyclohexane borylation. Because Ru-catalyzed borylation has not been theoretically investigated yet, its reaction mechanism was first elucidated; Cp*Ru(Bpin)3 1-Ru is an active species, and Cp*Ru(Bpin)3(H)(CH3) 4-Ru is a key intermediate. In 4-Ru, the Ru is understood to have an ambiguous oxidation state between +IV and +VI because it has a H··Bpin bonding interaction with a bond order of about 0.5. Methane borylation occurs through oxidative addition of methane C-H bond followed by reductive elimination of borylmethane in all of these catalysts. The catalytic activity for methane borylation increases following the order Cp*Ru(Bpin)3 < (TMPhen)Ir(Bpin)3 < Cp*Rh(Bpin)2. Cyclohexane borylation occurs in the same mechanism except for the presence of isomerization of a key intermediate. Chemoselectivity of methane over cyclohexane increases following the order Ir < Ru < Rh. In all of these catalysts, the rate-determining step (RDS) of cyclohexane borylation needs a larger ΔG°‡ than the RDS of methane borylation because the more bulky cyclohexyl group induces larger steric repulsion with the ligand than methyl. One reason for the worse chemoselectivity of the Ir catalyst is its less congested transition state of the reductive elimination of borylcyclohexane. Herein, use of a strongly electron-donating ligand consisting of pyridine and N-heterocyclic carbene with bulky substituents is computationally proposed as a good ligand for the Ir catalyst; actually, the Ir complex of this ligand is calculated to be more active and more chemoselective than Cp*Rh(Bpin)2 for methane borylation.

Control of local flexibility towards p-xylene sieving in Hofmann-type porous coordination polymers.

Adsorption-based xylene isomer separation is more energy efficient than conventional processes. Herein, three isostructural Hofmann-type porous coordination polymers (PCPs), {M(Pz)[Ni(CN)4]n} (M = Fe, FePzNi, Co, CoPzNi, and Ni, NiPzNi; Pz = pyrazine) were synthesized and shown to exhibit coordination-dependent lability for the selectivity toward p-xylene over m- and o-xylene.

Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling.

A new mode of bond activation involving M→Z interactions is disclosed. Coordination to transition metals as σ-acceptor ligands was found to enable the activation of fluorosilanes, opening the way to the first transition-metal-catalyzed Si-F bond activation. Using phosphines as directing groups, sila-Negishi couplings were developed by combining Pd and Ni complexes with external Lewis acids such as MgBr2. Several key catalytic intermediates have been authenticated spectroscopically and crystallographically. Combined with DFT calculations, all data support cooperative activation of the fluorosilane via Pd/Ni→Si-F→Lewis acid interaction with conversion of the Z-type fluorosilane ligand into an X-type silyl moiety.

Magnesiation of Aryl Fluorides Catalyzed by a Rhodium-Aluminum Complex.

We report the magnesiation of aryl fluorides catalyzed by an Al-Rh heterobimetallic complex. We show that the complex is highly reactive to cleave the C-F bonds across the polarized Al-Rh bond under mild conditions. The reaction allows the use of an easy-to-handle magnesium powder to generate a range of arylmagnesium reagents from aryl fluorides, which are conventionally inert to such metalation compared with other aryl halides.