Coinage Metal Complexes of a Sterically Encumbered Anionic Pyridylborate.

Sterically loaded, anionic pyridine has been synthesized and utilized successfully in the stabilization of a homoleptic series of coinage metal complexes.  The treatment of [4-(Ph3B)-2,6-Trip2Py]K (Trip =2,4,6-iPr3C6H2) with CuBr(PPh3), AgCl(PPh3) or AuCl(PPh3) (Py = pyridine) afforded the corresponding [4-(Ph3B)-2,6-Trip2Py]M(PPh3) (M = Au, Ag, Cu) complexes, via salt metathesis, as isolable, crystalline solids.  Notably, these reactions avoid the facile single electron transfer chemistry reported with the less bulky ligand systems.  The X-ray structures revealed that they are two-coordinate metal adducts.  The M-N and M-P bond distances are longest in the silver and shortest in the copper adduct among the three group 11 family members.  Computational analysis revealed an interesting stability dependence on steric bulk of the anionic pyridine (i.e., pyridyl borate) ligand.  A comparison of structures and bonding of [4-(Ph3B)-2,6-Trip2Py]Au(PPh3) to pyridine and m-terphenyl complexes, {[2,6-Trip2Py]Au(PPh3)}[SbF6] and [2,6-Trip2Ph]Au(PPh3) are also provided.  The Au(I) isocyanide complex, [4-(Ph3B)-2,6-Trip2Py]Au(CNBut) has been stabilized using the same anionic pyridylborate illustrating that it can support other gold-ligand moieties as well.

Going for gold - the chemistry of structurally authenticated gold(I)-ethylene complexes.

Gold coordination chemistry and catalysis involving unsaturated hydrocarbons such as olefins have experienced a remarkable growth during the last few decades. Despite the importance, isolable and well-characterized molecules with ethylene, the simplest and the most widely produced olefin, on gold are still limited. This review aims to cover features of, and strategies utilized to stabilize, gold-ethylene complexes and their diverse use in chemical transformations and homogeneous catalytic processes. Isolable and well-authenticated gold-ethylene complexes are important not only for structural, spectroscopic, and bonding studies but also as models for likely intermediates in gold mediated reactions of alkenes and gold-alkene species observed in the gas phase. There has also been development on AuI/III catalytic cycles. Nitrogen based ligands have been the most widely utilized ligand supports thus far for the successful stabilization of gold-ethylene adducts. Gold has a bright future in olefin chemistry and with ethylene.

Coinage metal-ethylene complexes of sterically demanding 1,10-phenanthroline ligands.

Phenanthroline-based ligands with bulky aryl groups flanking the metal binding pocket enabled the synthesis and detailed investigation of ethylene complexes of copper(I), silver(I), and gold(I), including structural data of [{2,9-bis(2,4,6-triisopropylphenyl)-1,10-phenanthroline}M(C2H4)][SbF6] (M = Cu, Ag, Au), Additionally, a related copper(I)-ethylene complex with a highly fluorinated ligand is also reported. Gold(I) affects the ethylene moiety significantly as evident from the notable upfield coordination shifts of ethylene carbon signals in the NMR and lengthening of the ethylene CC bond length. Silver(I) forms the weakest bond with ethylene in this series of isoleptic, group 11 metal-ethylene complexes. Preliminary catalytic investigations underscore the potential of copper complexes, particularly those with weakly coordinating supporting ligands, as effective catalysts for C(sp3)-H functionalization through trifluoromethyl carbene insertion.

Room Temperature Diels-Alder Reactions of 4-Vinylimidazoles.

In the course of studying Diels-Alder reactions of 4-vinylimidazoles with N-phenylmaleimide, it was discovered that they engage in cycloaddition at room temperature to give high yields of the initial cycloadduct as a single stereoisomer. In certain cases, the product precipitated out of the reaction mixture and could be isolated by simple filtration, thereby avoiding issues with aromatization observed during chromatographic purification. Given these results, intramolecular variants using doubly activated dienophiles were also investigated at room temperature. Amides underwent cycloaddition at room temperature in modest yields, but the initial adducts were not isolable with Nimid-benzyl-protected systems. Attempts to extend these results to the corresponding esters and hydroxamate were less successful with these substrates only undergoing cycloaddition at elevated temperatures in lower yields. Density functional theory calculations were performed to evaluate the putative transition states for both the inter- and intramolecular variants to rationalize experimental observations.

In situ studies of reversible solid-gas reactions of ethylene responsive silver pyrazolates.

Solid-gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF3)3Pz]Ag}3 and {[4-Br-3,5-(CF3)2Pz]Ag}3 supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF3)2Pz]Ag}3 under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above. Complete structural data of three novel silver-ethylene complexes are presented together with a thorough computational analysis of the mechanism.

Synthesis and Investigations of the Antitumor Effects of First-Row Transition Metal(II) Complexes Supported by Two Fluorinated and Non-Fluorinated ß-Diketonates.

The 3d transition metal (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes, supported by anions of sterically demanding ß-diketones, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3), were synthesized and evaluated for their antitumor activity. To assess the biological effects of substituents on phenyl moieties, we also synthesized and investigated the analogous metal(II) complexes of the anion of the less bulky 1,3-diphenylpropane-1,3-dione (HLPh) ligand. The compounds [Cu(LCF3)2], [Cu(LMes)2] and ([Zn(LMes)2]) were characterized by X-ray crystallography. The [Cu(LCF3)2] crystallizes with an apical molecule of solvent (THF) and features a rare square pyramidal geometry at the Cu(II) center. The copper(II) and zinc(II) complexes of diketonate ligands, derived from the deprotonated 1,3-dimesitylpropane-1,3-dione (HLMes), adopt a square planar or a tetrahedral geometry at the metal, respectively. We evaluated the antitumor properties of the newly synthesized (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) complexes against a series of human tumor cell lines derived from different solid tumors. Except for iron derivatives, cellular studies revealed noteworthy antitumor properties, even towards cancer cells endowed with poor sensitivity to the reference drug cisplatin.

Correction: When SF5 outplays CF3: effects of pentafluorosulfanyl decorated scorpionates on copper.

[This corrects the article DOI: 10.1039/D1SC04846E.].

Classical Gold Carbonyl Complexes in Tetrahedral and Trigonal-Planar Settings.

A unique four-coordinate, classical gold(I)-carbonyl complex with substantial backdonation from gold has been isolated by using a B-methylated and fluorinated tris(pyridyl)borate chelator. Its lighter silver(I) and copper(I) analogs enabled a study of trends in the coinage-metal family. The B-arylated ligand version also afforded a gold-carbon monoxide complex that displays a notably low C-O stretch value, but with trigonal planar geometry at the gold. A computational analysis shows that the AuI -CO bonds of these tris(pyridyl)borate ligand-supported molecules consist of electrostatic attraction, OC→Au σ-donation, and very significant Au→CO π-back-bonding components. The latter is responsible for the observed C-O stretching frequencies, which are lower than in free CO.

Understanding Copper(I)-Ethylene Bonding Using Cu K-Edge X-ray Absorption Spectroscopy.

Copper plays many important roles in ethylene chemistry, thus generating significant interest in understanding the structures, bonding, and properties of copper(I)-ethylene complexes. In this work, the ethylene binding characteristics of a series of isolable Cu(I)-ethylene compounds supported by a systematic set of fluorinated and nonfluorinated bis- and tris(pyrazolyl)borate and the related bis(pyrazolyl)methane ligands have been investigated. Through a combination of X-ray absorption spectroscopy and quantum chemical calculations, we characterize their geometric and electronic structures and the role that fluorinated ligands play in lowering the electron density at Cu sites. Such ligands increase the ethylene-to-Cu σ-donor interaction and, correspondingly, decrease the Cu-to-ethylene π back-bonding. This latter interaction leads to a partial vacancy in the Cu 3d level, which manifests experimentally as a low-energy feature in the Cu K pre-edge, allowing for its direct observation and comparison within a series of Cu(I) compounds. The pre-edge feature is reproduced by TD-DFT calculations, and its energy position and total intensity are used to quantitatively probe Cu-ethylene bonding. The variations in the Cu electronic structure influence the stability and overall ethylene bonding strength of these compounds, ultimately showing how substituents on the supporting ligands have a notable effect on their physical and chemical properties.

Thallium(I) Complexes of Tris(pyridyl)borates and a Comparison to Their Pyrazolyl Analogues.

Thallium(I) complexes of B-methylated and B-phenylated tris(pyridyl)borates featuring trifluoromethyl groups at the pyridyl ring 6-positions have been synthesized by metathesis using the corresponding potassium salts [MeB(6-(CF3)Py)3]K and [PhB(6-(CF3)Py)3]K with thallium(I) acetate. The closely related tris(pyrazolyl)borate analogue [PhB(3-(CF3)Pz)3]Tl has also been prepared, and comparisons of structural and spectroscopic features between the two scorpionate families are presented. [MeB(6-(CF3)Py)3]Tl displays κ3-coordination of the tris(pyridyl)borate similar to that of tris(pyrazolyl)borate in [MeB(3-(CF3)Pz)3]Tl, while [PhB(6-(CF3)Py)3]Tl and [PhB(3-(CF3)Pz)3]Tl feature κ2-N,N ligand coordination modes with the B-phenyl groups flanking the thallium sites. 19F NMR spectroscopy of [MeB(6-(CF3)Py)3]Tl reveals the presence of a remarkably large 1208 Hz four-bond thallium-fluorine coupling constant in chloroform at room temperature, which is considerably larger than 878 Hz observed for the pyrazolyl borate analogue [MeB(3-(CF3)Pz)3]Tl. Although [PhB(6-(CF3)Py)3]Tl is structurally nonrigid at room temperature in chloroform, at lower temperatures, the ligand arm exchange slows down, revealing 4JTl-F = 1110 Hz. Steric demands of these ligands have been quantified using the buried volume concept. In addition, ligand transfer chemistry from [MeB(6-(CF3)Py)3]Tl and [PhB(6-(CF3)Py)3]Tl to copper(I) under ethylene and computational analyses of the various coordination modes of tris(pyrazolyl)borates and tris(pyridyl)borates are reported.

Filling the gap with a bulky diaryl boron group: fluorinated and non-fluorinated copper pyrazolates fitted with a dimesityl boron moiety on the backbone.

Successful synthesis has been reported of 4-Mes2B-3,5-(CF3)2PzH and 4-Mes2B-3,5-(CF3)2PzH bearing sterically demanding diarylboron moieties at the pyrazole ring 4-position, and their corresponding copper(I) pyrazolate complexes. They show visible blue photoluminescence in solution. The X-ray crystal structures revealed that the fluorinated {[4-BMes2-3,5-(CF3)2Pz]Cu}3 crystallizes as discrete trinuclear molecules whereas as the non-fluorinated {[4-BMes2-3,5-(CH3)2Pz]Cu}3 forms dimers of trimers with two close inter-trimer Cu⋯Cu separations. The solid {[4-BMes2-3,5-(CF3)2Pz]Cu}3 featuring a sterically confined Cu3N6 core displays bright blue phosphorescence while {[4-BMes2-3,5-(CH3)2Pz]Cu}3, which is a dimer of a trimer, is a red phosphor at room temperature. This work illustrates the modulation of photo-physical properties of metal pyrazolates by adjusting the supporting ligand steric features and introducing secondary diarylboron luminophores. Computational analysis of the structures and photophysical properties of copper complexes are also presented.

Synthesis and cytotoxicity studies of Cu(I) and Ag(I) complexes based on sterically hindered ß-diketonates with different degrees of fluorination.

Design, synthesis, and in vitro antitumor properties of Cu(I) and Ag(I) phosphane complexes supported by the anions of sterically hindered ß-diketone ligands, 1,3-dimesitylpropane-1,3-dione (HLMes) and 1,3-bis(3,5-bis(trifluoromethyl)phenyl)-3-hydroxyprop-2-en-1-one (HLCF3) featuring trifluoromethyl or methyl groups on the phenyl moieties have been reported. In order to compare the biological effects of substituents on the phenyl moieties, the analogous copper(I) and silver(I) complexes of the anion of the parent 1,3-diphenylpropane-1,3-dione (HLPh) ligand were also synthesized and included in the study. In the syntheses of the Cu(I) and Ag(I) complexes, the phosphane coligands triphenylphosphine (PPh3) and 1,3,5-triaza-7-phosphaadamantane (PTA) were used to stabilize silver and copper in the +1 oxidation state, preventing the metal ion reduction to Ag(0) or oxidation to Cu(II), respectively. X-ray crystal structures of HLCF3 and the metal adducts [Cu(LCF3)(PPh3)2] and [Ag(LPh)(PPh3)2] are also presented. The antitumor properties of both classes of metal complexes were evaluated against a series of human tumor cell lines derived from different solid tumors, by means of both 2D and 3D cell viability studies. They display noteworthy antitumor properties and are more potent than cisplatin in inhibiting cancer cell growth.

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators.

Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu4][MeBF3]. These N-based ligands permitted the isolation of group 11 metal-ethylene complexes [MeB(6-(CF3)Py)3]M(C2H4) and [Me2B(6-(CF3)Py)2]M(C2H4) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene 13C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal-ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF3)Py)3]M(C2H4) adopt the rare κ2 coordination mode rather than the typical κ3 coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ2 coordination mode is favored over the κ3-mode in these coinage metal-ethylene complexes and point to the effects CF3-substituents have on κ2/κ3-energy difference. The M-C and M-N bond distances of [MeB(6-(CF3)Py)3]M(C2H4) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene-M interaction energy of κ2-[MeB(6-(CF3)Py)3]M(C2H4) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.

Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu(I) pyrazolate cyclotrimers.

Described herein are the synthesis, structure, and photophysics of the iodo-substituted cyclic trinuclear copper(I) complex, Cu3[4-I-3,5-(CF3)2Pz]3 supported by a highly-fluorinated pyrazolate in comparison with its previously reported 4-Br/4-Cl analogues. The crystal structure is stabilised by multiple supramolecular interactions of Cu3⋯I and hydrogen/halogen bonding. The photophysical properties and supramolecular interactions are investigated experimentally/computationally for all three 4-halo complexes vis-à-vis relativistic effects.

Remarkably Selective Propylene-Propane Separation Using a Copper Scorpionate.

Propylene is a crucial building block to produce many industrial-scale chemicals including polypropylene. The separation of propylene from propane to reach the high-purity levels needed for downstream applications is a difficult task due to the close similarities in their physical properties. The olefin/paraffin separation including that involving propylene mainly relies on highly energy-intensive distillation processes and accounts for nearly 0.3% of the global energy consumption. The utility of a copper complex supported by a fluorinated bis(pyrazolyl)borate is demonstrated to accomplish the separation of propylene from propane repeatedly, under mild conditions with high selectivity. Complete characterization of a rare, copper(I) propylene complex is also reported including the molecular structure.

Bonding and 13 C-NMR properties of coinage metal tris(ethylene) and tris(norbornene) complexes: Evaluation of the role of relativistic effects from DFT calculations.

The π-complexes of cationic coinage metal ions (Cu(I), Ag(I), Au(I)) provide useful experimental support for understanding fundamental characteristics of bonding and 13 C-NMR patterns of the group 11 triad. Here, we account for the role of relativistic effects on olefin-coinage metal ion interaction for cationic, homoleptic tris-ethylene, and tris-norbornene complexes, [M(η2 -C2 H4 )3 ]+ and [M(η2 -C7 H10 )3 ]+ (M = Cu, Ag, Au), as representative case of studies. The M-(CC) bond strength in the cationic, tris-ethylene complexes is affected sizably for Au and to a lesser extent for Ag and Cu (48.6%, 16.7%, and 4.3%, respectively), owing to the influence on the different stabilizing terms accounting for the interaction energy in the formation of coinage metal cation-π complexes. The bonding elements provided by olefin → M σ-donation and olefin ← M π-backbonding are consequently affected, leading to a lesser covalent interaction going down in the triad if the relativistic effects are ignored. Analysis of the 13 C-NMR tensors provides further understanding of the observed experimental values, where the degree of backbonding charge donation to π2 *-olefin orbital is the main influence on the observed high-field shifts in comparison to the free olefin. This donation is larger for ethylene complexes and lower for norbornene counterparts. However, the bonding energy in the later complexes is slightly stabilized given by the enhancement in the electrostatic character of the interaction. Thus, the theoretical evaluation of metal-alkene bonds, and other metal-bonding situations, benefits from the incorporation of relativistic effects even in lighter counterparts, which have an increasing role going down in the group.

Isolable acetylene complexes of copper and silver.

Copper and silver play important roles in acetylene transformations but isolable molecules with acetylene bonded to Cu(i) and Ag(i) ions are scarce. This report describes the stabilization of π-acetylene complexes of such metal ions supported by fluorinated and non-fluorinated, pyrazole-based chelators. These Cu(i) and Ag(i) complexes were formed readily in solutions under an atmosphere of excess acetylene and the appropriate ligand supported metal precursor, and could be isolated as crystalline solids, enabling complete characterization using multiple tools including X-ray crystallography. Molecules that display κ2-or κ3-ligand coordination modes and trigonal planar or tetrahedral metal centers have been observed. Different trends in coordination shifts of the acetylenic carbon resonance were revealed by 13C NMR spectroscopy for the Cu(i) and Ag(i) complexes. The reduction in acetylene [italic small nu, Greek, macron] C[triple bond, length as m-dash]C due to metal ion coordination is relatively large for copper adducts. Computational tools were also used to quantitatively understand in detail the bonding situation in these species. It is found that the interaction between the transition metal fragment and the acetylene ligand is significantly stronger in the copper complexes, which is consistent with the experimental findings. The C[triple bond, length as m-dash]C distance of these copper and silver acetylene complexes resulting from routine X-ray models suffers due to incomplete deconvolution of thermal smearing and anisotropy of the electron density in acetylene, and is shorter than expected. A method to estimate the C[triple bond, length as m-dash]C distance of these metal complexes based on their experimental [italic small nu, Greek, macron] C[triple bond, length as m-dash]C is also presented.

Bonding situation in isolable silver(I) carbonyl complexes of the Scorpionates.

The bonding situation of Ag(I)CO complexes having a Scorpionate ligand directly attached to the transition metal has been analyzed in detail by means of relativistic density functional theory calculations. To this end, different experimentally characterized complexes together with other representative species have been considered to rationalize the observed shift of the corresponding ν(CO) stretching frequencies and the influence of the substituents in the Scorpionate ligand. With the help of the energy decomposition analysis method combined with the natural orbital for chemical valence it is found that the main contribution to the bonding comes from the electrostatic attractions between the LAg(I) and CO fragments. Despite that, the LAg â†’ CO π-backdonation is also significant in these species as well as in related LCu(I)CO complexes.