Metal-ligand Cooperation Research Articles

Ruthenium-Catalyzed Dehydrogenative Functionalization of Alcohols to Pyrroles: A Comparison between Metal-Ligand Cooperative and Non-cooperative Approaches.

Herein, we report the synthesis and characterization of two ruthenium-based pincer-type catalysts, [1]X (X = Cl, PF6) and 2, containing two different tridentate pincer ligands, 2-pyrazolyl-(1,10-phenanthroline) (L1) and 2-arylazo-(1,10-phenanthroline) (L2a/2b, L2a = 2-(phenyldiazenyl)-1,10-phenanthroline; L2b = 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline), and their application in the synthesis of substituted pyrroles via dehydrogenative alcohol functionalization reactions. In catalyst [1]X (X = Cl, PF6), the tridentate scaffold 2-pyrazolyl-(1,10-phenanthroline) (L1) is apparently redox innocent, and all the redox events occur at the metal center, and the coordinated ligands remain as spectators. In contrast, in catalysts 2a and 2b, the coordinated azo-aromatic scaffolds are highly redox-active and known to participate actively during the dehydrogenation of alcohols. A comparison between the catalytic activities of these two catalysts was made, starting from the simple dehydrogenation of alcohols to further dehydrogenative functionalization of alcohols to various substituted pyrroles to understand the advantages/disadvantages of the metal-ligand cooperative approach. Various substituted pyrroles were prepared via dehydrogenative coupling of secondary alcohols and amino alcohols, and the N-substituted pyrroles were synthesized via dehydrogenative coupling of aromatic amines with cis-2-butene-1,4-diol and 2-butyne-1,4-diol, respectively. Several control reactions and spectroscopic experiments were performed to characterize the catalysts and establish the reaction mechanism.

Dehydrogenation of formic acid mediated by a Phosphorus–Nitrogen PN3P-manganese pincer complex: Catalytic performance and mechanistic insights

The utilization of formic acid as a liquid organic hydrogen carrier has taken a vast interest lately because of several desirable properties. The state-of-the-art homogenous catalysts known for formic acid dehydrogenation are mainly based on noble metals such as iridium or ruthenium. 3d metals are considered to be an attractive alternative due to their abundance and low toxicity. Exploration of 3d metals has achieved exciting results mainly with iron-based catalysts; however, manganese has not received much attention, and only a few examples are available. Here we report a manganese complex [Mn(PN3P)(CO)2]Br containing a pincer backbone, as an efficient catalyst for formic acid dehydrogenation. Under the optimized condition, the complex afforded a TON of 15,200. To the best of our knowledge, this is considered one of the best TON achieved using a manganese-based complex with excellent selectivity. Mechanistic studies suggested that the imine arm participates in the formic acid activation/deprotonation step, emphasizing the importance of metal-ligand cooperativity during substrate activation to promote catalytic efficacy.

Cooperative C-H Bond Activation by a Low-Spin d6 Iron-Aluminum Complex.

The reactions of transition metal complexes underpin numerous synthetic processes and catalytic transformations. Typically, this reactivity involves the participation of empty and filled molecular orbitals centered on the transition metal. Kinetically stabilized species, such as octahedral low-spin d6 transition metal complexes, are not expected to participate directly in these reactions. However, novel approaches that exploit metal–ligand cooperativity offer an opportunity to challenge these preconceptions. Here, we show that inclusion of an aluminum-based ligand into the coordination sphere of neutral low-spin d6 iron complex leads to unexpected reactivity. Complexes featuring an unsupported Fe–Al bond are capable of the intermolecular C–H bond activation of pyridines. Mechanistic analysis suggests that C–H activation proceeds through a reductive deprotonation in which the two metal centers (Fe and Al) act like a frustrated Lewis pair. The key to this behavior is a ground state destabilization of the d6 iron complex, brought about by the inclusion of the electropositive aluminum-based ligand. These findings have immediate implications for the design of reagents and catalysts based on first-row transition metals.

Metal-Ligand Cooperativity in Iron Dinitrogen Complexes: Proton-Coupled Electron Transfer Disproportionation and an Anionic Fe(0)N2 Hydride.

Metal-ligand cooperativity and redox-active ligands enable the use of open-shell first-row transition metals in catalysis. However, the fleeting nature of the reactive intermediates prevents direct inspection of the relevant catalytic species. By employing phosphine α-iminopyridine (PNN)-based complexes, we show that chemical and redox metal-ligand cooperativity can be combined in the coordination sphere of iron dinitrogen complexes. These systems show dual activation modes either through deprotonation, which triggers reversible core dearomatization, or through reversibly accepting one electron by reducing the imine functionality. (PNN)Fe(N2) fragments can be obtained under mildly reducing conditions. Deprotonation of such complexes induces dearomatization of the pyridine core while retaining a terminally coordinated N2 ligand. This species is nevertheless stable in solution only below -30 °C and undergoes unusual ligand-assisted redox disproportionation through proton-coupled electron transfer at room temperature. The origin of this phenomenon is the significant lability of the α-imine C-H bonds in the dearomatized species, where the calculated bond dissociation free energy is 48.7 kcal mol-1. The dispropotionation reaction yields an overreduced iron compound, demonstrating that the formation of such species can be triggered by mild bases, and does not require harsh reducing agents. Reaction of the dearomatized species with dihydrogen yields a rare anionic Fe hydride that binds dinitrogen and features a rearomatized core.

Low-Valent Molybdenum PNP Pincer Complexes as Catalysts for the Semihydrogenation of Alkynes.

Low-valent molybdenum PNP pincer complexes were studied as catalysts for the semihydrogenation of alkynes. For that purpose, tBu-substituted PNP complexes PNPtBuMo(CO)2 (6a) and PNPtBuMo(CO)3 (6c) and the NNP complex NNPiPrMo(CO)2(PPh3) ((rac)-7) were synthesized and characterized. By utilizing the cyclohexyl-substituted complex PNPCyMo(CO)2(CH3CN) (5a), several diphenylacetylene derivatives are transformed to the corresponding (Z)-alkenes with good to very good diastereoselectivities (up to 91:9). Mechanistic experiments indicate an outer-sphere mechanism including metal–ligand cooperativity.

Three Isomeric Zn(II)-Sn(IV)-Zn(II) Porphyrin-Triad-Based Supramolecular Nanoarchitectures for the Morphology-Dependent Photocatalytic Degradation of Methyl Orange.

Three isomeric Zn(II)–Sn(IV)–Zn(II) porphyrin-based triads (T2, T3, and T4) were synthesized by the reaction of common Zn(II) porphyrins (ZnL) with different Sn(IV) porphyrins (SnPn). The Sn(IV) porphyrin precursors differ with respect to the position of the pyridyl-N atoms. All compounds were characterized by 1H NMR, UV–vis, fluorescence spectroscopy, electrospray ionization–mass spectrometry, and field-emission scanning electron microscopy measurements. In these structures, the intramolecular cooperative metal–ligand coordination of the 3-pyridyl nitrogen in SnP3 with axial ZnL and the π–π interactions between the adjacent porphyrin triad are the determining factors affecting the nanostructures of T3. Owing to the geometrical constraints of the SnP2 center, this type of interaction is not possible for T2. Therefore, only the π–π interactions affect the self-assembly process. In the case of SnP4, intermolecular coordinative interactions and then π–π interactions are responsible for the nanostructure of T4. The morphology-dependent photocatalytic degradation of methyl orange (MO) dye in aqueous solution under visible light irradiation was observed for these photocatalysts, and the degradation ratio of MO varied from 76 to 94% within 100 min. Nanorod-shaped T3 exhibited higher performance compared to nanosphere T2 and nanoflake T4.

Acceleration Effect of Bases on Mn Pincer Complex-Catalyzed CO2 Hydroboration

Herein, we report a comprehensive study of CO2 hydroboration catalyzed by Mn pincer complexes. The traditional metal-ligand cooperation (MLC) mechanism based on the H-Mn-N-Bpin pincer complex is not viable due to the competing abstraction of the Bpin group from the H-Mn-N-Bpin complex by NaOtBu. Instead, we propose an ionic mechanism based on the H-Mn-N-Na species with a low energy span (22.5 kcal/mol) and unveil the acceleration effect of bases. The X groups in the H-Mn-N-X catalyst models are further modulated, and the steric hindrance and H→B donor-acceptor interactions of the X group increase the energy barrier of the hydride transfer. The hydrogen bond and electrostatic interactions of the X group can accelerate the hydride transfer to HCOOBpin and HCHO molecules except for the nonpolar CO2 molecule. Based on these discoveries, we designed a pyridine-based Mn pincer catalyst system, which could achieve CO2 hydroboration in low-temperature and base-free conditions through a metal-ligand cooperation mechanism.

Cleavage of Si–H and Si–C Bonds by Metal–Ligand Cooperation: Formation of Silyl Anion and Silylene Equivalents from Tertiary Silanes

The cleavage of silicon–hydrogen bonds to generate silicon-containing metal complexes has played an essential role in the preparation of organosilicon compounds. Herein, we report the reaction of cyclopentadienone iridium complex 1 with hydrosilanes to afford hydroxycyclopentadienyl iridium silyl complexes 4 via the umpolung of the Si–H bond. The nucleophilicity of the Ir–Si bond in the resulting complex was demonstrated in the reaction with an allyl halide and ethyl acrylate. Furthermore, a silylene complex was formed from hydroxycyclopentadienyl silyliridium complex 4 via the formal reductive elimination of the C–H bond at the silicon center to release benzene. The silylene complex synthesized from tricarbylsilane showed ambiphilic reactivities, which are consistent with the classical reactivities of silylenes.

Hydration of Nitriles Enabled by PNP−manganese Pincer Catalyst

AbstractA general and practical methodology for the hydration of nitriles to primary amides enabled by manganese catalyst is presented. The described protocol shows broad substrate scope with good functional group tolerance, including a wide range of (hetero)aromatic and aliphatic nitriles, thus afforded the corresponding amides in good to excellent isolated yields under mild conditions. Preliminary mechanistic studies indicated that metal‐ligand cooperation (MLC) mode was involved in this catalytic process.

Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

The chemistry of frustrated Lewis pair (FLP) is widely explored in the activation of small molecules, the hydrogenation of CO2, and unsaturated organic species. A survey of several experimental works on the activation of small molecules by FLPs and the related mechanistic insights into their reactivity from electronic structure theory calculation are provided in the present review, along with the catalytic hydrogenation of CO2. The mechanistic insight into H2 activation is thoroughly discussed, which may provide a guideline to design more efficient FLP for H2 activation. FLPs can activate other small molecules like, CO, NO, CO2, SO2, N2O, alkenes, alkynes, etc. by cooperative action of the Lewis centers of FLPs, as revealed by several computational analyses. The activation barrier of H2 and other small molecules by the FLP can be decreased by utilizing the aromaticity criterion in the FLP as demonstrated by the nucleus independent chemical shift (NICS) analysis. The term boron-ligand cooperation (BLC), which is analogous to the metal-ligand cooperation (MLC), is invoked to describe a distinct class of reactivity of some specific FLPs towards H2 activation.

Iron-Catalyzed Metal-Ligand Cooperative Approach toward Sustainable Synthesis of Azines and N-Acylhydrazones in Air.

Herein, we describe a metal-ligand cooperative approach for the sustainable synthesis of various aldazines, ketazines, and N-acylhydrazones via dehydrogenative functionalization of alcohols with hydrazine hydrate using a simple, easy-to-prepare iron catalyst featuring a redox noninnocent tridentate arylazo backbone. Our catalyst is compatible with both primary and secondary alcohols to produce a wide variety of substituted aldazines, ketazines, and N-acylhydrazones in good isolated yields in air. A series of control experiments are performed to elucidate the reaction mechanism.

Quantifying Variations in Metal-Ligand Cooperative Binding Strength with Cyclic Voltammetry and Redox-Active Ligands.

Metal-ligand cooperativity (MLC), a phenomenon that leverages reactive ligands to promote synergistic reactions with metals, has proven to be a powerful approach to achieving new and unprecedented chemical transformations with metal complexes. While many examples of MLC are known with a wide range of substrates, experimentally quantifying how ligand modifications affect MLC binding strength remains a challenge. Here we describe how cyclic voltammetry (CV) was used to quantify differences in MLC binding strength in a series of square-pyramidal Ru complexes. This method relies on using multifunctional ligands (those capable of both MLC and ligand-centered redox activity) as electrochemical reporters of MLC binding strength. The synthesis and characterization of Ru complexes with three different redox-active tetradentate ligands and two different ancillary phosphines (PPh3 and PCy3) are described. Titration CV studies conducted using BH3·THF with BH3 as a model MLC substrate allowed ΔGMLC to be quantified for each complex. Compared to our base triaryl ligand, increasing π conjugation in the backbone of the redox-active ligand enhanced MLC binding, whereas increasing π conjugation in the flanking groups decreased the MLC binding strength. Structures and spectroscopic data collected for the isolated MLC complexes are also described along with supporting DFT calculations that were used to illuminate electronic factors that likely account for the observed differences in the MLC binding strength. These results demonstrate how redox-active ligands and CV can be used to quantify subtle differences in the MLC binding strength across a series of structurally related complexes with different ligand modifications.

Metal complexes containing silicon‐based pincer ligands: Reactivity and application in small molecule activation

AbstractThis review highlights the chemical properties of metal complexes supported by silicon‐based tridentate ligands. Silicon donors coordinated to a metal exhibit unique characteristics such as a strong trans influence, σ‐SiH interaction, and metal–ligand cooperativity. Thus, this type of donors ensures distinct reactivity toward various substrates. In particular, the σ‐SiH interaction and mechanism of SiH bond cleavage are discussed. Several attempts to exploit silyl metal complexes for the activation of small molecules, including dinitrogen, carbon dioxide, dihydrogen, and dioxygen, have been reported. This review summarizes recently reported reactions of silyl pincer complexes with small molecules and provides new insights into the possibility of adapting silicon‐based ligands to model the chemistry of biological catalytic systems.

Computational mechanistic studies of ruthenium catalysed methanol dehydrogenation.

Homogeneous ruthenium catalysed methanol dehydrogenation could become a key reaction for hydrogen production in liquid fuel cells. In order to improve existing catalytic systems, mechanistic insight is paramount in directing future studies. Herein, we describe what computational mechanistic research has taught us so far about ruthenium catalysed dehydrogenation reactions. In general, two mechanistic pathways can be operative in these reactions: a metal-centered or a metal–ligand cooperative (Noyori–Morris type) minimum energy reaction pathway (MERP). Discerning between these mechanisms on the basis of computational studies has proven to be highly input dependent, and to circumvent pitfalls it is important to consider several factors, such as solvent effects, metal–ligand cooperativity, alternative geometries, and complex electronic structures of metal centres. This Frontiers article summarizes the reported computational research performed on ruthenium catalyzed dehydrogenation reactions performed in the past decade, and serves as a guide for future research.

Cooperative B-H bond activation: dual site borane activation by redox active κ2-N,S-chelated complexes.

Cooperative dual site activation of boranes by redox-active 1,3-N,S-chelated ruthenium species, mer-[PR3{κ2-N,S-(L)}2Ru{κ1-S-(L)}], (mer-2a: R = Cy, mer-2b: R = Ph; L = NC7H4S2), generated from the aerial oxidation of borate complexes, [PR3{κ2-N,S-(L)}Ru{κ3-H,S,S′-BH2(L)2}] (trans–mer-1a: R = Cy, trans–mer-1b: R = Ph; L = NC7H4S2), has been investigated. Utilizing the rich electronic behaviour of these 1,3-N,S-chelated ruthenium species, we have established that a combination of redox-active ligands and metal–ligand cooperativity has a big influence on the multisite borane activation. For example, treatment of mer-2a–b with BH3·THF led to the isolation of fac-[PR3Ru{κ3-H,S,S′-(NH2BSBH2N)(S2C7H4)2}] (fac-3a: R = Cy and fac-3b: R = Ph) that captured boranes at both sites of the κ2-N,S-chelated ruthenacycles. The core structure of fac-3a and fac-3b consists of two five-membered ruthenacycles [RuBNCS] which are fused by one butterfly moiety [RuB2S]. Analogous fac-3c, [PPh3Ru{κ3-H,S,S′-(NH2BSBH2N)(SC5H4)2}], can also be synthesized from the reaction of BH3·THF with [PPh3{κ2-N,S-(SNC5H4)}{κ3-H,S,S′-BH2(SNH4C5)2}Ru], cis–fac-1c. In stark contrast, when mer-2b was treated with BH2Mes (Mes = 2,4,6-trimethyl phenyl) it led to the formation of trans- and cis-bis(dihydroborate) complexes [{κ3-S,H,H-(NH2BMes)Ru(S2C7H4)}2], (trans-4 and cis-4). Both the complexes have two five-membered [Ru–(H)2–B–NCS] ruthenacycles with κ2-H–H coordination modes. Density functional theory (DFT) calculations suggest that the activation of boranes across the dual Ru–N site is more facile than the Ru–S one.

Vanadium pyridonates: dimerization, redox behaviour, and metal-ligand cooperativity.

The synthesis, structure, and reactivity of vanadium pyridonate complexes are described. Vanadium(III) pyridonate complexes were accessed through protonolysis and reduction of a tetrakis(amido)vanadium(IV) starting material. Bis(pyridonate) vanadium(IV) precursors could be isolated depending on the amount of proteoligand added. The targeted vanadium(III) species tend to form dimers, but monomeric complexes can be achieved in the presence of neutral donors such as amines or pyridine derivatives or through the use of sterically demanding proligands. The reduction process is proposed to involve dimeric intermediates and be mediated by the amine released from protonolysis, thereby forming the corresponding imine as a byproduct. Isolated amine complexes of vanadium(III) are presented. In contrast, bis(amidate)vanadium(IV) complexes were not found to undergo a similar reduction. This work informs on design principles for the synthesis and application of new vanadium pyridonate catalysts for transformations involving dimerization and PCET for changes in oxidation state.

Combining metal-metal cooperativity, metal-ligand cooperativity and chemical non-innocence in diiron carbonyl complexes.

Several metalloenzymes, including [FeFe]-hydrogenase, employ cofactors wherein multiple metal atoms work together with surrounding ligands that mediate heterolytic and concerted proton–electron transfer (CPET) bond activation steps. Herein, we report a new dinucleating PNNP expanded pincer ligand, which can bind two low-valent iron atoms in close proximity to enable metal–metal cooperativity (MMC). In addition, reversible partial dearomatization of the ligand's naphthyridine core enables both heterolytic metal–ligand cooperativity (MLC) and chemical non-innocence through CPET steps. Thermochemical and computational studies show how a change in ligand binding mode can lower the bond dissociation free energy of ligand C(sp3)–H bonds by ∼25 kcal mol−1. H-atom abstraction enabled trapping of an unstable intermediate, which undergoes facile loss of two carbonyl ligands to form an unusual paramagnetic (S = ) complex containing a mixed-valent iron(0)–iron(i) core bound within a partially dearomatized PNNP ligand. Finally, cyclic voltammetry experiments showed that these diiron complexes show catalytic activity for the electrochemical hydrogen evolution reaction. This work presents the first example of a ligand system that enables MMC, heterolytic MLC and chemical non-innocence, thereby providing important insights and opportunities for the development of bimetallic systems that exploit these features to enable new (catalytic) reactivity.

Heterolytic cleavage of a Si-H bond by a metal-ligand cooperation of a cationic iridium amido complex and hydrosilylation of aldehydes.

Heterolytic cleavage of a Si-H bond was achieved mediated by a metal-ligand cooperation of a cationic iridium amido complex. The reaction was applied to the catalytic hydrosilylation of benzaldehyde and its derivatives, affording the corresponding hydrosilylated products in moderate to good yields.

Controlled monodefluorination and alkylation of C(sp3)-F bonds by lanthanide photocatalysts: importance of metal-ligand cooperativity.

The controlled functionalization of a single fluorine in a CF3 group is difficult and rare. Photochemical C-F bond functionalization of the sp3-C-H bond in trifluorotoluene, PhCF3, is achieved using catalysts made from earth-abundant lanthanides, (CpMe4)2Ln(2-O-3,5- t Bu2-C6H2)(1-C{N(CH)2N(iPr)}) (Ln = La, Ce, Nd and Sm, CpMe4 = C5Me4H). The Ce complex is the most effective at mediating hydrodefluorination and defluoroalkylative coupling of PhCF3 with alkenes; addition of magnesium dialkyls enables catalytic C-F bond cleavage and C-C bond formation by all the complexes. Mechanistic experiments confirm the essential role of the Lewis acidic metal and support an inner-sphere mechanism of C-F activation. Computational studies agree that coordination of the C-F substrate is essential for C-F bond cleavage. The unexpected catalytic activity for all members is made possible by the light-absorbing ability of the redox non-innocent ligands. The results described herein underscore the importance of metal-ligand cooperativity, specifically the synergy between the metal and ligand in both light absorption and redox reactivity, in organometallic photocatalysis.

Cooperative approaches in catalytic hydrogenation and dehydrogenation.

Metal-ligand cooperativity (MLC) is an established strategy for developing effective hydrogenation and dehydrogenation catalysts. Metal-metal cooperativity (MMC) in bimetallic complexes is not as well understood, and to date has had limited implementation in (de)hydrogenation. Herein we use (de)hydrogenation processes as a platform to examine modes of cooperativity, with a particular focus on catalytic mechanisms. We investigate how lessons learnt from the extensive development of metal-ligand cooperative catalysts can aid the ongoing development of metal-metal cooperative catalysts.