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A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu2(μ-Cl)2(PNNN)] (1). In contrast, complexation of [RuCl2(cymene)]2 yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ2-N,N, rather than κ2-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl3(cymene)(PNNN)] (3) and [RuCuCl2(cymene)(PNNN)]2[PF6]2 ([4]2[PF6]2), which both exhibit κ1-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation–aromatisation behaviour at the metal–ligand cooperative methylene site upon sequential treatment with base (KOtBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ2-P,N. [ABSTRACT FROM AUTHOR]

The Chemical Communications journal, published by The Royal Society of Chemistry, features articles on various topics such as catalytic enantioselective construction, microbial transformation of heavy metals, and alkyne annulations. The journal also covers topics like photoswitches, ammonia adsorption, and selective photocatalytic CO2 reduction. Additionally, the journal includes articles on topics like thiazole synthesis, redox platforms, and lanthanide coordination polymers. The publication aims to uncover new possibilities and provide fundamental answers to scientific questions. [Extracted from the article]

We report the synthesis of a heterobimetallic U(III)–Ir species which reacts with CS2 to form the novel ethanetetrathiolate fragment via hydride insertion and C–C coupling. Computational studies suggest the formation of a radical intermediate, which may couple with another equivalent to form the final product. [ABSTRACT FROM AUTHOR]

A series of heterobimetallic complexes Au/M (M = RhIII, IrIII) were prepared on the basis of two ditopic ligands: a monophosphane ligand L1H and a triphosphane ligand L2H. The complexes were fully characterised, including single-crystal X-ray diffraction studies. Catalytic activity of cationic L1/AuI/IrIII and L2/AuI/IrIII bis(trifluoromethane)sulfonimide was analysed through their capacity to induce allenyl ether rearrangement and cycloisomerisation of N-propargyl benzamide. While cationic L1/AuI/IrIII showed some ability to induce allenyl ether rearrangement, no conversion was observed for cationic L2/AuI/IrIII. Similarly, N-propargyl benzamide could undergo cycloisomerisation in the presence of cationic L1/AuI/IrIII, whereas cationic L2/AuI/IrIII was again inactive. These findings highlight how crucial the surroundings of the metal centre are to the catalytic activity. Catalytic activity is only possible when Au has a free coordination site; the gold complex becomes inactive when the tridentate ligand is present. [ABSTRACT FROM AUTHOR]

Heterobimetallic complexes are studied for their ability to mimic biological systems as well as active sites in heterogeneous catalysts. While specific interest in early/late heterobimetallic systems has fluctuated, they serve as important models to fundamentally understand metal–metal bonding. Specifically, the polarized metal–metal multiple bonds formed in highly reduced early/late heterobimetallic complexes exemplify how each metal modulates the electronic environment and reactivity of the complex as a whole. In this Perspective, we chronicle the development of phosphinoamide-supported group IV/cobalt heterobimetallic complexes. This combination of metals allows access to a low valent Co−I center, which performs a rich variety of bond activation reactions when coupled with the pendent Lewis acidic metal center. Conversely, the low valent late transition metal is also observed to act as an electron reservoir, allowing for redox processes to occur at the d0 group IV metal site. Most of the bond activation reactions carried out by phosphinoamide-bridged M/Co−I (M = Ti, Zr, Hf) complexes are facilitated by cleavage of metal–metal multiple bonds, which serve as readily accessible electron reservoirs. Comparative studies in which both the number of buttressing ligands as well as the identity of the early metal were varied to give a library of heterobimetallic complexes are summarized, providing a thorough understanding of the reactivity of M/Co−I heterobimetallic systems. [ABSTRACT FROM AUTHOR]

Reactions of 2,6‐dipicolinoylbis(N,N‐diethylthiourea) (H2LEt) with common tellurium(IV) starting materials such as PhTeBr3 or TeBr4 yield various tellurium(IV) and tellurium(II) compounds depending on the conditions applied. Equimolar amounts of H2LEt and PhTeBr3 give the 1 : 1 complex [PhTeIVBr3(H2LEt)], while with an excess of H2LEt, the tellurium compound is partially reduced and a {PhTeII}+ building block coordinates to both sulfur atoms of H2LEt under the formation of the ion pair [PhTeII(H2LEt)][PhTeIVBr4]. Similar reactions between H2LEt and TeBr4 give the neutral monomer [TeIIBr2(H2LEt)] or the coordination polymer [TeIIBr2(H2LEt)]∞. The latter compound is also formed with the assistance of Pb2+ ions. While the lead ions do not appear in the isolated product, similar reactions with transition metal ions such as Ni2+, Mn2+, or Co2+ result in the formation of heterobimetallic complexes, in which Te(II) building blocks are directed to the sulfur atoms of the deprotonated ligand {H2LEt2‐S,S}2−, while the transition metal ions occupy central coordination positions between two of the organic ligands using the pyridine nitrogen atom, carbonyl oxygen atom(s) and/or the nitrogen atoms of the thiourea units. [ABSTRACT FROM AUTHOR]

Alkali–metal nickelates are a class of highly reactive heterobimetallic complexes derived from Ni(0)–olefins and polar organo-alkali–metal reagents. First reported over 50 years ago, it is only in recent years that these overlooked complexes have found formidable roles in sustainable catalysis and beyond. In this article, we will showcase the emerging catalytic applications of lithium nickelates and discuss the mechanisms by which these heterobimetallic complexes facilitate challenging cross-coupling reactions. We will also review the unique structure and bonding of alkali–metal nickelates, as interrogated by X-ray crystallography and complementary bonding analysis, and finally explore the diverse coordination and co-complexation chemistry of these heterobimetallic complexes. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

The reduction of titanocene dichloride Cp2TiCl2 with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [Cp2Ti] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [Cp2TiCl]-type complexes, including the structurally characterized heterobimetallic complex [Cp2Ti(μ-Cl)2SmCl2(THF)3]. These results were corroborated by reactivity studies (alkyne coupling and radical reactions), EPR spectroscopy and electrospray mass spectrometry, providing new insights into the reduction chemistry of lanthanide metals. [ABSTRACT FROM AUTHOR]

Hydrogenations are fundamentally and industrially important reactions that are atom economical paths to synthesize value‐added products from feedstock chemicals. The cooperative effects of two or more metal centers in multimetallic active sites is a successful strategy to activate small molecules and facilitate catalytic reactions, and this strategy has been recently applied to catalytic hydrogenation reactions. Furthermore, heterobimetallic complexes have been well‐documented to provide novel reaction pathways and improved selectivity, compared to their homo‐bimetallic and monometallic analogues. This minireview provides a historical perspective on the development of heterobimetallic catalysts for the hydrogenation of unsaturated substrates and describes recent developments in this burgeoning research area. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Establishing unprecedented types of bonding interactions is one of the fundamental challenges in synthetic chemistry, paving the way to new (electronic) structures, physicochemical properties, and reactivity. In this context, unsupported element‐element interactions are particularly noteworthy since they offer pristine scientific information about the newly identified structural motif. Here we report the synthesis, isolation, and full characterization of the heterobimetallic Bi/Pt compound [Pt(PCy3)2(BiMe2)(SbF6)] (1), bearing the first unsupported transition metal→bismuth donor/acceptor interaction as its key structural motif. 1 is surprisingly robust, its electronic spectra are interpreted in a fully relativistic approach, and it reveals an unprecedented reactivity towards H2. [ABSTRACT FROM AUTHOR]

Context: The field of chemistry has significantly evolved, with catalysis playing a crucial role in transforming chemical processes. From Valerius' use of sulfuric acid in the sixteenth century to modern advancements, catalysis has driven innovations across various industries. The introduction of gold as a catalyst marked a pivotal shift, expanding its applications beyond ornamentation to homogeneous catalysis. Gold's unique properties, such as its electrophilic nature and flexibility, have enabled its use in synthesizing complex molecules, including those in nanomedicine and sustainable chemical processes. The development of gold-based complexes, particularly in hydroalkoxylation and hydroamination reactions, showcases their efficiency in forming carbon–oxygen bonds under mild conditions. Recent studies on dual gold catalysis and heterobimetallic complexes further highlight gold's versatility in achieving high turnover rates and selectivity. This evolution underscores the potential of gold catalysis in advancing environmentally sustainable methodologies and enhancing the scope of modern synthetic chemistry. The debate about the nature of monogold and dual-gold catalysis is open. Methods: DFT calculations have played a key role in promoting the activation of alkynes, in particular the hydrophenoxylation of alkynes by metal-based catalysts. They not only help identify the most efficient and selective catalysts but also aid in screening for those capable of performing a dual metal catalytic mechanism. The most commonly used functionals are BP86 and B3LYP, with the SVP and 6-31G(d) basis sets employed for geometry optimizations, and M06 with TZVP or 6-311G(d,p) basis sets used for single-point energy calculations in a solvent. Grimme dispersion correction has been explicitly added either in the solvent single point energy calculations or in the gas phase geometry optimizations or in both. To point out that M06 implicitly includes part of this dispersion scheme. [ABSTRACT FROM AUTHOR]

The heterobimetallic complexes [{Pd(PPh3)2(4-Epy)2}{Cu(PPh3)2Cl}2] (E = S, Se) were synthesized from the CuI complex [CuCl(PPh3)3] and "metallo-ligands" [PdCl(PPh3)2(4-Epy)] (1) and [Pd(PPh3)2(4-Epy)2] (2) (Epy− = 4-pyridylchalcogenolate; E = S or Se). Reaction of 2, having two free pyridyl groups, yields a cleaner product than 1, possessing only one pyridyl group. NMR spectroscopy, ESI-MS spectrometry and X-ray diffraction structures are in line with centrosymmetric molecules, a square planar PdII center and two tetrahedral CuI centers, that are bridged by two trans oriented 4-pyridylchalcogenolates. The same reaction using the chelating diphosphine ligand dppf resulted in insoluble products. The two mixed metal PdII–CuI complexes show high catalytic activity in the Sonogashira cross-coupling reactions of phenylacetylene and a variety of aryl bromides. The optimized reaction produced a TON of 470 000 and a TOF of 31 300 h−1. [ABSTRACT FROM AUTHOR]

A yet‐outstanding supramolecular chemistry challenge is isolation of novel varieties of stacked complexes with finely‐tuned donor‐acceptor bonding and optoelectronic properties, as herein reported for binary adducts comprising two different cyclic trinuclear complexes (CTC@CTC'). Most previous attempts focused only on 1–2 factors among metal/ligand/substituent combinations, resulting in heterobimetallic complexes. Instead, here we show that, when all 3 factors are carefully considered, a broadened variety of CTC@CTC' stacked pairs with intuitively‐enhanced intertrimer coordinate‐covalent bonding strength and ligand‐ligand/metal‐ligand dispersion are attained (dM–M' 2.868(2) Å; ΔE>50 kcal/mol, an order of magnitude higher than aurophilic/metallophilic interactions). Significantly, CTC@CTC' pairs remain intact/strongly‐bound even in solution (Keq 4.67×105 L/mol via NMR/UV‐vis titrations), and the gas phase (mass spectrometry revealing molecular peaks for the entire CTC@CTC' units in sublimed samples), rather than simple co‐crystal formation. Photo‐/electro‐luminescence studies unravel metal‐centered phosphorescence useful for novel all metal‐organic light‐emitting diodes (MOLEDs) optoelectronic device concepts. This work manifests systematic design of supramolecular bonding and multi‐faceted spectral properties of pure metal‐organic macrometallacyclic donor/acceptor (inorganic/inorganic) stacks with remarkably‐rich optoelectronic properties akin to well‐established organic/organic and organic/inorganic analogues. [ABSTRACT FROM AUTHOR]

This review focuses on the synthetic inorganic chemistry of structural and functional models of Mo-Cu CO dehydrogenase (CODH). Mo-Cu CODH is an aerobic enzyme that catalyzes CO oxidation. The active site of Mo-Cu CODH demonstrates a structural motif unprecedented in inorganic chemistry: dithiolene-ligated MoVIO2S linked to a two-coordinate Cu(I) through a single bridging sulfido, {MoVIO2(μ2-S)CuI}. There is significant interest in understanding how this unusual active site structure enables reactivity. Structural analogues of varying accuracy have been reported by several research groups and are discussed in this review. Most of the modeling chemistry indicates that the single sulfido-bridged MoVI-(μ2-S)-CuI structure is unstable when the metals are coordinatively unsaturated, generally collapsing into the stable MoVI-(μ2-S)2-CuI or MoVI-(μ2-S)(μ2-O)-CuI diamond cores outside of the protein environments. Whereas singly bridged {MoVIO2(μ2-S)CuI} oxidizes CO and inserts CNR (isocyanide) efficiently, no biomimetic CODH-relevant reactivity was observed for the synthetic analogues containing the aforementioned diamond cores. An alternative synthetic approach pursuing a "bioinspired" functional model is also discussed. In this approach, two relevant metal sites (hypothesized to be primarily responsible for the reactivity) are combined into a heterobimetallic complex using appropriate heterodinucleating ligands. Syntheses, structures, and cooperative bimetallic reactivity of these heterobimetallic complexes will be discussed. [ABSTRACT FROM AUTHOR]

The selective synthesis of biomimetic Fe/Mn complexes able to mimic the geometry and catalytic activity of enzymes possessing this cofactor is still a challenge. Herein, we discuss the stepwise synthesis, characterization, and magnetic properties of a Fe(II)/Mn(II) species and related Fe(II)/Fe(II) complexes. [ABSTRACT FROM AUTHOR]

A novel Ta/Os heterobimetallic complex, [Ta(CH2tBu)3(μ-H)3OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH2tBu)3 with Cp*OsH5. Treatment of 2 and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], 1, with CO2 under mild conditions reveal the efficient cleavage of CO2, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H2 and Cp*Os(CO)H3, respectively. This bimetallic reactivity diverges from more classical CO2 insertion into metal–X (X = metal, hydride, alkyl) bonds. [ABSTRACT FROM AUTHOR]

The document is the contents list for an issue of the journal Chemical Communications. It includes the titles and authors of various articles and features that will be included in the issue. Some of the topics covered include silk-based intelligent fibers and textiles, advances in molecular engineering of perovskite heterostructures, and metal-organic framework based self-powered devices for human body energy harvesting. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp=2,6‐N,N′‐diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, C6F5). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one‐pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties. [ABSTRACT FROM AUTHOR]

Silver indium selenide (AgInSe2) has been proposed as an efficient absorber material for sustainable solar cells. Phase pure preparation of this exotic material in the nano regime is highly desirable. This report describes the design and synthesis of a new heterobimetallic complex [(Ph3P)2Ag(μ-SeCH2Ph)2In(SeCH2Ph)2] along with its structural characterization. This complex acts as an air enduring, normal temperature and pressure (NTP) stable versatile single source precursor for synthesizing bulk, nanocrystalline and thin film of AgInSe2. The crystal structure, phase purity, morphology, elemental composition and band gap of the synthesized materials were determined from powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and diffuse reflectance spectroscopy (DRS-UV), respectively. The band gap of the nanocrystalline AgInSe2 lies in the range suitable for solar cell applications. A prototype photoelectrochemical cell fabricated with the pristine AgInSe2 nanoparticles exhibits high photoresponsivity, which makes them a suitable candidate for clean energy applications. [ABSTRACT FROM AUTHOR]

A general synthetic procedure to neutral homo- and heterobimetallic cage compounds exhibiting various structural motifs of the polypnictogen ligands starting from [Cp*Fe(η5-E5)] (E = P (1), As (2); Cp* = C5Me5) is reported. The impact of the implemented transition metal precursors {Cp′′′M} (M = Cr, Mn, Fe, Ni; Cp′′′ = 1,2,4-tBu3C5H2) emphasises the variability of the isolated complexes exhibiting a broad variety of structural motifs of the pnictogen ligands. Spectroscopic, crystallographic, and theoretical investigations provide insight into the structure of the partially unprecedented polypnictogen ligands. [ABSTRACT FROM AUTHOR]

Complexes featuring multiple metal centres are of growing interest regarding metal–metal cooperation and its tuneability. Here the synthesis and characterisation of heterobimetallic complexes of a 3d metal (4: Mn, 5: Co) and lanthanum supported by a (1,1,1-tris[(3-methoxysalicylideneamino)methyl]ethane) ligand is reported, as well as discussion of their electronic structure via electron paramagnetic resonance (EPR) spectroscopy, electrochemical experiments and computational studies. Competitive binding experiments of the ligand and various metal salts unequivocally demonstrate that in these heterobimetallic complexes the 3d metal (Mn, Co) selectively occupies the κ6-N3O3 binding site of the ligand, whilst La occupies the κ6-O6 metal binding site in line with their relative oxophilicities. EPR spectroscopy supported by density functional theory analysis indicates that the 3d metal is high spin in both cases (S = 5/2 (Mn), 3/2 (Co)). Cyclic voltammetry studies on the Mn/La and Co/La bimetallic complexes revealed a quasi-reversible Mn2+/3+ redox process and poorly-defined irreversible oxidation events respectively. [ABSTRACT FROM AUTHOR]

Early/late heterobimetallic complexes are widely recognized as one of the most effective catalysts for activating coupling reactions. Herein, DFT calculations were used to investigate the specific mechanisms of terminal alkyne dimerization facilitated by two types of Zr/Co complexes: the bis (phosphinoamide) complex B and the mono (phosphinoamide) complex C. In addition, their reaction activities were compared with that of three ligand‐bridged Zr/Co complex A. The results show that the activated mechanisms of the three reactions are similar, all of them contain inner‐ and outer‐sphere mechanisms, and the inner one is the optimal process. Compared to A, the terminal alkyne dimerizations activated by B and C have the lower energy barriers and better selectivity for the E‐isomer; thus, the mono‐ and bis‐(phosphinoamide) Zr/Co complexes are expected to show better activity and selectivity than tris (phosphinoamide) complexes. The stereoselectivity of E‐, Z‐, and gem‐isomers is controlled by the reductive elimination process. The IRI analysis reveals that the selectivity for E‐ and Z‐isomers is influenced due to the notable repulsion and vdW interaction between the second alkyne and the MeNPMe2 ligand. Our work provides a theoretical basis for experimental applications and offers inspiration for the design of high selectivity heterobimetallic complexes. [ABSTRACT FROM AUTHOR]

Low-valent nickelates have recently been shown to be key intermediates in challenging cross-coupling reactions using aryl ethers as electrophiles. Key for the success of these transformations is the activation of the substrate through π-coordination to the nickelate intermediate, however there is still limited knowledge about the fundamental structure and coordination chemistry of these heterobimetallic complexes. Herein, we report the synthesis, structures, and spectroscopic analysis of a diverse family of alkali–metal nickelates derived from phenyl-alkali–metal reagents and Ni(ttt-CDT), where ttt-CDT = trans,trans,trans-1,5,9-cyclododecatriene. The co-complexation of PhLi with Ni(ttt-CDT) was found to yield 1 : 1, 2 : 1 or 4 : 2 lithium nickelates depending on the stoichiometry and reaction conditions employed. The high lability of the ttt-CDT ligand enables facile ligand exchange with an assorted series of organic π-acceptors, ranging from polyaromatic hydrocarbons to ketones, imines and nitriles. For anthracene and phenanthrene, a homologous series of Li, Na and K nickelates could be obtained, which lead to different structural motifs or degrees of aggregation in the solid-state spanning solvated monomers to complex polymeric arrangements. For π-extended systems such as perylene or coronene, competing single-electron-transfer to give the corresponding radical anions was observed, illustrating the highly reducing nature of the alkali–metal nickelates. X-ray crystallographic analysis and NMR spectroscopy of the phenyl-alkali–metal nickelates reveal extreme back-bonding from Ni(0) to the organic π-acceptors due to strong σ-donation from the carbanionic ligands. [ABSTRACT FROM AUTHOR]

Novel heterobimetallic complexes of type [Zn(L)2M2(R)4Cl2], where M = Sn(IV) and Si(IV); R = –CH3 and –C6H5, were prepared by reacting the methanolic solution of monometallic complex [Zn(L)2Cl2] with group fourteen organometallic dichloride [(CH3)2SnCl2/(C6H5)2SnCl2/(CH3)2SiCl2/(C6H5)2SiCl2]. The structures of the obtained complexes were identified by various spectrometric methods such as Fourier transformation infra-red (FT-IR), nuclear magnetic resonance (NMR), electrospray ionization mass spectrometry, powder X-ray diffraction, molar conductivity, and UV–Vis. Density functional theory (DFT) calculations were performed to explore the quantum chemical properties of the newly designed Zn(II) complexes. In vitro antimicrobial, anti-inflammatory, and anticancer activities of Schiff base ligand [L], mononuclear complex [Zn(L)2Cl2] and its corresponding heterobimetallic complexes, [Zn(L)2M2(R)4Cl2], were evaluated. The heterobimetallic complexes exhibited higher activities against Gram-positive bacteria (Bacillus Subtilis and Bacillus cereus), Gram-negative bacteria (Xanthomonas Campestris and Pseudomonas aeruginosa), and fungal strains (Aspergillus flavus and Fusarium oxysporum) in comparison with both the Schiff base ligand and the monometallic complex. This enhanced performance of the heterobimetallic complexes can be attributed to the synergistic effect. The heterobimetallic complex [Zn(L)2Sn2(C6H5)4Cl2] showed the highest potential of inflammation inhibition with IC50 = 5.2 µg/mL, very close to standard drug sodium diclofenac (IC50 = 4.59 µg/mL). Furthermore, the synthesized compounds were assessed for their anticancer activity against three cell lines: human colon (HCT-116), human breast (MDA-MB-231), and human lung cancer cells (A549) using the MTT assay. The obtained results showed that the heterobimetallic complex [Zn(L)2Sn2(C6H5)4Cl2] displayed the highest cytotoxic activity (IC50 = 3.12 ± 0.25, 3.72 ± 0.26, and 3.94 ± 0.14 for HCT-116, MDA-MB-231 and A549, respectively). These findings suggest that the newly formulated metal complexes could be explored further in the pursuit of drug development. [ABSTRACT FROM AUTHOR]

Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including 1H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond. Carbaporphyrin dimers, known for their interesting photophysical properties and application in metal-organic chemistry, generally contain two identical subunits. Here, the authors highlight the benefits that can accrue from breaking the inherent symmetry of carbaporphyrin dimers and details a new approach to creating heterobimetallic complexes. [ABSTRACT FROM AUTHOR]

Recent advances on low valent main group metal chemistry have shown the excellent potential of heterobimetallic complexes derived from Al(I) to promote cooperative small molecule activation processes. A signature feature of these complexes is the use of bulky chelating ligands which act as spectators providing kinetic stabilization to their highly reactive Al−M bonds. Here we report the synthesis of novel Al/Zn bimetallics prepared by the selective formal insertion of AlCp* into the Zn−N bond of the utility zinc amides ZnR2 (R=HMDS, hexamethyldisilazide; or TMP, 2,2,6,6‐tetramethylpiperidide). By systematically assessing the reactivity of the new [(R)(Cp*)AlZn(R)] bimetallics towards carbodiimides, structural and mechanistic insights have been gained on their ability to undergo insertion in their Zn−Al bond. Disclosing a ligand effect, when R=TMP, an isomerization process can be induced giving [(TMP)2AlZn(Cp*)] which displays a special reactivity towards carbodiimides and carbon dioxide involving both its Al−N bonds, leaving its Al−Zn bond untouched. [ABSTRACT FROM AUTHOR]

We report a straightforward alkane elimination strategy to prepare well-defined heterobimetallic Al/Mo species. Notably, the reaction of the monohydride complex of molybdenum, Cp*MoH(CO)3, with triisobutyl aluminum affords a new heterobimetallic [MoAl]2 tetranuclear compound, [Cp*Mo(CO)(µ-CO)2Al(iBu)2]2, (1), featuring a 12-membered C4O4Mo2Al2 ring in which isocarbonyls bridge the Mo and Al centers. The addition of pyridine to this complex successfully results in the dissociation of the dimer into a new discrete binuclear complex, [Cp*Mo(CO)2(µ-CO)Al(Py)(iBu)2], (2). Switching the nature of the Lewis base from pyridine to tetrahydrofuran does not lead to the THF analogue of adduct 2, but rather to a complex reaction where one of the identified products corresponds to a tetranuclear species, [Cp*Mo(CO)3(μ-CH2CH2CH2CH2O)Al(iBu)2]2, (3), featuring two bridging alkoxybutyl fragments originating from the C-O ring opening of THF. Compound 3 adds to the unusual occurrences of THF ring opening by heterobimetallic complexes, which is evocative of masked metal-only frustrated Lewis pair behavior and highlights the high reactivity of these Al/Mo assemblies. [ABSTRACT FROM AUTHOR]

The controlled formation of mixed-metal bimetallics was realised through use of a fac-[Re(CO)3(N,N′-bpy-P)Cl] complex bearing an exogenous 2,4,6-trioxa-1,3,5,7-tetramethyl-8-phosphaadamantane donor at the 5-position of the bpy. The introduction of gold, silver, and rhodium with appropriate secondary ligands was readily achieved from established starting materials. Restricted rotation about the C(bpy)-P bond was observed in several of the bimetallic complexes and correlated with the relative steric bulk of the second metal moiety. Related chemistry with the 6-substituted derivative proved more limited in scope with only the bimetallic Re/Au complex being isolated. [ABSTRACT FROM AUTHOR]

Literature reports have demonstrated that Schiff-base-type ligands can serve as robust platforms for the synthesis of heterobimetallic complexes containing transition metals and the uranyl dication (UO22+). However, efforts have not advanced to include either synthesis of complexes containing second- or third-row transition metals or measurement of the redox properties of the corresponding heterobimetallic complexes, despite the significance of actinide redox in studies of nuclear fuel reprocessing and separations. Here, metalloligands denoted [Ni], [Pd], and [Pt] that contain the corresponding Group 10 metals have been prepared and a synthetic strategy to access species incorporating the uranyl ion (UO22+) has been explored, toward the goal of understanding how the secondary metals could tune uranium-centered redox chemistry. The synthesis and redox characterization of the bimetallic complex [Ni,UO2] was achieved, and factors that appear to govern extension of the chosen synthetic strategy to complexes with Pd and Pt are reported here. Infrared and solid-state structural data from X-ray diffraction analysis of the metalloligands [Pd] and [Pt] show that the metal centers in these complexes adopt the expected square planar geometries, while the structure of the bimetallic [Ni,UO2] reveals that the uranyl moiety influences the coordination environment of Ni(II), including inducement of a puckering of the ligand backbone of the complex in which the phenyl rings fold around the nickel-containing core in an umbrella-shaped fashion. Cyclic voltammetric data collected on the heterobimetallic complexes of both Ni(II) and Pd(II) provide evidence for uranium-centered redox cycling, as well as for the accessibility of other reductions that could be associated with Ni(II) or the organic ligand backbone. Taken together, these results highlight the unique redox behaviors that can be observed in multimetallic systems and design concepts that could be useful for accessing tunable multimetallic complexes containing the uranyl dication. [ABSTRACT FROM AUTHOR]

With the goal of generating hetero‐redox levels on metals as well as on nitric oxide (NO), metallodithiolate (N2S2)CoIII(NO−), N2S2 = N,N‐ dibenzyl‐3,7‐diazanonane‐1,9‐dithiolate, is introduced as ligand to a well‐characterized labile [Ni0(NO)+] synthon. The reaction between [Ni0(NO+)] and [CoIII(NO−)] has led to a remarkable electronic and ligand redistribution to form a heterobimetallic dinitrosyl cobalt [(N2S2)NiII∙Co(NO)2]+ complex with formal two electron oxidation state switches concomitant with the nickel extraction or transfer as NiII into the N2S2 ligand binding site. To date, this is the first reported heterobimetallic cobalt dinitrosyl complex. [ABSTRACT FROM AUTHOR]

We describe a family of cationic methylstannylene and chloro‐ and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn:+ are stabilized by coordination to PtII and are formed by facile Me group transfer from dimethyl or monomethyl PtII complexes, in the latter case triggered by concomitant B−H, Si−H, and H2 bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl− removal from HSiCl3 under ambient conditions. The computational studies show that stabilization of cationic methylstannylenes and cationic silylenes is achieved through weak coordination to a neutral N‐donor ligand binding pocket. The analysis of the electronic potentials, as well as the Laplacian of electron density, also reveals the differences in the character of Pt−Si vs. Pt−Sn bonding. We demonstrate the importance of a ligand‐supported binuclear Pt/tetrel core and weak coordination to facilitate access to tetrylium‐ylidene Pt complexes, and a transmetalation approach to the synthesis of MeSnII:+ derivatives. [ABSTRACT FROM AUTHOR]

This manuscript describes the syntheses, structures and magnetism of MnIII–CaII/SrII complexes which are compositionally relevant in the context of the oxygen evolving complex (OEC) of photosystem II (PS II). A series of trimetallic tetraoxo complexes containing redox-inactive metal ions CaII or SrII were synthesized using a tetranucleating ligand framework. The structural characteristics of these complexes, with the oxido ligands bridging the redox-inactive metals and the manganese centres, make them particularly relevant to biological and heterogeneous metal-oxido clusters. Electrochemical studies of these compounds show that the reduction potentials are highly dependent upon the Lewis acidity of the redox-inactive metal, identifying the chemical basis for the observed differences in electrochemistry. This correlation provides insights into the role of the CaII/SrII ion in modulating the redox potential of the OEC and of other redox-inactive ions in tuning the redox potentials of other metal-oxide electrocatalysts. Temperature dependent magnetic measurements have also been performed for the complexes. [ABSTRACT FROM AUTHOR]

This manuscript describes the syntheses, structures and magnetism of MnIII–CaII/SrII complexes which are compositionally relevant in the context of the oxygen evolving complex (OEC) of photosystem II (PS II). A series of trimetallic tetraoxo complexes containing redox-inactive metal ions CaII or SrII were synthesized using a tetranucleating ligand framework. The structural characteristics of these complexes, with the oxido ligands bridging the redox-inactive metals and the manganese centres, make them particularly relevant to biological and heterogeneous metal-oxido clusters. Electrochemical studies of these compounds show that the reduction potentials are highly dependent upon the Lewis acidity of the redox-inactive metal, identifying the chemical basis for the observed differences in electrochemistry. This correlation provides insights into the role of the CaII/SrII ion in modulating the redox potential of the OEC and of other redox-inactive ions in tuning the redox potentials of other metal-oxide electrocatalysts. Temperature dependent magnetic measurements have also been performed for the complexes. [ABSTRACT FROM AUTHOR]

Alkenes are an important class of organic molecules found among synthetic intermediates and bioactive compounds. They are commonly synthesized through stoichiometric Wittig‐type olefination of carbonyls and imines, using ylides or their equivalents. Despite the importance of Wittig‐type olefination reactions, their catalytic variants remain underdeveloped. We explored the use of transition metal catalysis to form ylide equivalents from readily available starting materials. Our investigation led to a new copper‐catalyzed olefination of imines with alkenyl boronate esters as coupling partners. We identified a heterobimetallic complex, obtained by hydrocupration of the alkenyl boronate esters, as the key catalytic intermediate that serves as an ylide equivalent. The high E‐selectivity observed in the reaction is due to the stereoselective addition of this intermediate to an imine, followed by stereospecific anti‐elimination. [ABSTRACT FROM AUTHOR]

The direct activation of C–H bonds has been a rich and active field of organometallic chemistry for many years. Recently, incredible progress has been made and important mechanistic insights have accelerated research. In particular, the use of heterobimetallic complexes to heterolytically activate C–H bonds across the two metal centers has seen a recent surge in interest. This perspective article aims to orient the reader in this fast moving field, highlight recent progress, give design considerations for further research and provide an optimistic outlook on the future of catalytic C–H functionalization with heterobimetallic complexes. [ABSTRACT FROM AUTHOR]

Electrocatalytic and photocatalytic CO2 reduction by a heterobimetallic Cu/Fe–Mabiq complex were examined and compared to the monometallic [Fe(Mabiq)]+. The neighbouring Cu–Xantphos unit leads to marked changes in the electrocatalytic mechanism and enhanced photocatalytic performance. [ABSTRACT FROM AUTHOR]

In luminescent devices, the combination of red, green, and blue luminophores (RGB system) allows the creation of other colours in the electromagnetic spectrum, including the perception of white light. Among the three fundamental colours necessary to create the RGB system, normally, the red colour has received great attention compared with the others because red luminophores present lower Φ due to the energy gap law. Red emitters are easily obtained using EuIII ion, however, although the red emitters based on the EuIII ion have high colour purity, the Φ normally is lower compared with red emitters based on the IrIII ion, even though the colour purity of the latter is not so high. Thus, to produce efficient red-emitting complexes, a strategy that has been developed is the synthesis of heterobimetallic d–f complexes to join the high Φ of the d-metal complexes with the high colour purity of the EuIII ion. Herein, a novel dual bimetallic emitter was synthesised and fully characterised, the [{Ir(dfppy)2(μ-bpdc)}3Eu2]Cl3·nH2O·mCH3OH (dfppy is the 2-(2,4-difluorophenyl)pyridine cyclometallating ligand, and the ancillary ligand bpdc is the 2,2′bipyridine-3,3′-dicarboxylic acid). This complex was immobilised in a polymeric PMMA film presenting a high Φ value, 42.2 ± 4.2%, in the yellow spectral region. Its precursor, the novel green-emitting IrIII complex, [Ir(dfppy)2(bpdc)], showed 97.2 ± 9.7% of Φ after doped in PMMA matrix. Both films were used to coat a UV-LED chip to investigate the photophysical properties when these complexes are applied to create phosphor-converted LEDs. The bimetallic prototype exhibited higher radiant photostability after 18 h of operation compared with the heteroleptic IrIII complex-doped film. For the first time, the lowest triplet energy (19 103 cm−1) from an IrIII complex that efficiently sensitises the EuIII ion in an IrIII–EuIII heterobimetallic complex has been determined using voltage modulation in a UV-coated LED prototype, which can be used to engineer new pure red-emitting d–f bimetallic systems. [ABSTRACT FROM AUTHOR]

A series of furan-2-thiocarboxylate complexes of indium(III), Et3NH[In(SCOf)4] (1), iPr2NH2[In(SCOf)4] (2), [In(2,2′-bipy)(SCOf)3] (3a), and [In(1,10-phen)(SCOf)3] (3b), have been synthesized and structurally characterized. Complex 4, [In(TMEDA)(SCOf)(SH)2], was obtained by the partial hydrolysis of [In(TMEDA)(SCOf)3] (3). Heterobimetallic complexes [(SCOf)2In(μ-SCOf)2Cu(PPh3)2] (5) and [(SCOf)2In(μ-SCOf)2Ag(PPh3)2] (6), were also synthesized and characterized. In an attempt to synthesize the binary compound, In(SCOf)3 (7), a thioester fCOSCH2SCOf (8) was obtained serendipitously; thus, a novel convenient approach for thioester synthesis is introduced. The catalytic activities of all the complexes were assessed for Knoevenagel condensation and Knoevenagel initiated MCRs for the synthesis of chromene and imidazopyrimidine derivatives and it was found that complex 2 is a very efficient catalyst (much superior to the previously reported ones). [ABSTRACT FROM AUTHOR]

The reaction of DyCl3 with two equivalents of [Li(THF)n]2[DADMe2] [DADMe2 = 2,6-Pri2C6H3NC(Me)· C(Me)NC6H3Pri2-2,6] affords the ate-complex [Li(THF)4][Dy(DADMe2)2] in 71% yield. X-Ray analysis revealed that this complex presents a separated ion pair in which the Dy3+ ion is coordinated by two dianionic ene-diamide ligands. [ABSTRACT FROM AUTHOR]

Abstract With the goal of generating hetero‐redox levels on metals as well as on nitric oxide (NO), metallodithiolate (N2S2)CoIII(NO−), N2S2 = N,N‐ dibenzyl‐3,7‐diazanonane‐1,9‐dithiolate, is introduced as ligand to a well‐characterized labile [Ni0(NO)+] synthon. The reaction between [Ni0(NO+)] and [CoIII(NO−)] has led to a remarkable electronic and ligand redistribution to form a heterobimetallic dinitrosyl cobalt [(N2S2)NiII∙Co(NO)2]+ complex with formal two electron oxidation state switches concomitant with the nickel extraction or transfer as NiII into the N2S2 ligand binding site. To date, this is the first reported heterobimetallic cobalt dinitrosyl complex.

We report herein the first nonheme CuFe oxygen reduction catalyst ([CuII(bpbp)(μ‐OAc)2FeIII]2+, CuFe−OAc), which serves as a functional model of cytochrome c oxidase and can catalyze oxygen reduction to water with a turnover frequency of 2.4×103 s−1 and selectivity of 96.0 % in the presence of Et3NH+. This performance significantly outcompetes its homobimetallic analogues (2.7 s−1 of CuCu−OAc with %H2O2 selectivity of 98.9 %, and inactive of FeFe−OAc) under the same conditions. Structure‐activity relationship studies, in combination with density functional theory calculation, show that the CuFe center efficiently mediates O−O bond cleavage via a CuII(μ‐η1 : η2‐O2)FeIII peroxo intermediate in which the peroxo ligand possesses distinctive coordinating and electronic character. Our work sheds light on the nature of Cu/Fe heterobimetallic cooperation in oxygen reduction catalysis and demonstrates the potential of this synergistic effect in the design of nonheme oxygen reduction catalysts. [ABSTRACT FROM AUTHOR]

The bis(azolium) salt [L1‐H2]Br2 was found to serve as a suitable platform for accessing the heterobimetallic IrIII‐M (M=PdII/AuI) and PdII‐IrIII complexes. Initially, selective mono‐metalation of [L1‐H2]Br2 yielded an orthometalated IrIII‐ or non‐orthometalated PdII‐complex. Sequential metalation of the mono‐IrIII complex resulted in the formation of heterobimetallic IrIII‐PdII/AuI complexes. Similarly, a distinct heterobimetallic PdII‐IrIII complex was synthesized starting from the mono‐PdII complex. Further, the corresponding homobimetallic IrIII‐IrIII and PdII‐PdII complexes were directly obtained from [L1‐H2]Br2. Additionally, monometallic PdII and IrIII analogues were synthesized from [L2‐H]Br and [L3‐H]Br, respectively. The heterobimetallic IrIII‐PdII and PdII‐IrIII complexes were then evaluated as catalysts in various one‐pot tandem catalytic reactions in which they demonstrated superior activity than the mixtures of both their corresponding homobimetallic IrIII‐IrIII/PdII‐PdII and monometallic IrIII/PdII counterparts, under the constant concentrations of metal centers. Moreover, while comparing complexes IrIII‐PdII and PdII‐IrIII, the former exhibits higher activity in all the studied reactions. All these findings suggest the presence of some form of cooperativity between the two metal centers (Ir and Pd) connected by a single ligand framework in IrIII‐PdII and PdII‐IrIII complex, with IrIII‐PdII displaying better cooperativity that has been validated by electrochemical, NMR, and DFT studies. [ABSTRACT FROM AUTHOR]

A heterobimetallic complex [MeN(CH2CH2NPiPr)2MgLiCl(THF)]2 (1) supported by a dianionic double layer nitrogen–phosphorus ligand was synthesized by the reaction of H2L1 (H2L1 = MeN(CH2CH2NHPiPr)2) with MgCl2 in the presence of n-BuLi. Reactions of complex 1 with 2 equivalents of CuI, AgI and AuCl·SMe2 led to the formation of heterobimetallic clusters [MeN(CH2CH2NPiPr)2MgCuI]2 (2), [MeN(CH2CH2NPiPr)2MgAgI]2 (3) and [MeN(CH2CH2NPiPr)2MgAuCl]2 (4), respectively. X-ray single-crystal diffraction analysis revealed that these complexes are dimers, which are composed of two [MeN(CH2CH2NPiPr)2Mg] units connected by coinage metals (i.e., Cu, Ag, and Au). The reactivity of 1 was further investigated and it was found that complex 1 could react with 4 equivalents of MeI, giving a complex [CH3N(CH2CH2N＝PiPr2Me)2MgI]+[I]− (5), which can be viewed as a magnesium complex supported by a neutral double layer nitrogen–phosphorus ligand (CH3N(CH2CH2N＝PiPr2Me)2). Complex 1 could also react with 2 equivalents of NaNH2, leading to the isolation of an amido anion bridged magnesium–sodium heterobimetallic cluster [MeN(CH2CH2NPiPr)2MgNaNH2]2 (6). [ABSTRACT FROM AUTHOR]

The newly designed trinuclear heterobimetallic complexes [Ni(L)2(M)2R4Cl2] were synthesized by using methanolic solution of mononuclear Ni(II) complex and various organometallic dichlorides (where L = 3,4-diaminobenzophenone (C13H12N2O), M = Sn(IV), Si(IV), Ti(IV), and Zr(IV), and R = Ph, Me, C5H5, C4H9, etc.). The synthesized complexes were characterized on the basis of physicochemical and spectral (FTIR, UV–visible, 1H-NMR, 13C-NMR, 29Si-NMR, 119Sn-NMR, Mass, and PXRD) studies. IR spectroscopy confirmed the coordination of -NH2 group to the metal centre. PXRD patterns show the crystalline nature of all the synthesized complexes. Among the synthesized complexes, mononuclear metal complex adopted square planar geometry while trinuclear heterobimetallic complexes adopted distorted octahedral geometry. This geometry is also supported by DFT calculations. The in vitro antimicrobial effectiveness of these resulting compounds has been scrutinized against a number of bacterial strains (Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus gordonii, and Bacillus cereus) by the agar disc diffusion method and fungal strains (Aspergillus flavus and Penicillium funiculosum) by the disc diffusion method and promising results were attained. The synthesized complexes were also evaluated for their DNA binding studies, antioxidant, and anti-inflammatory activities. The DPPH• scavenging activity of the synthesized complexes determines their antioxidant behaviour. The pharmacologically accessed in vitro anti-inflammatory activity by the protein denaturation method was also investigated. The results indicated better biological activities of heterobimetallic complexes than the monometallic complex. In addition, ANOVA and Tukey's test for the experimental results of biological activities for all the synthesized complexes supported the significant difference in the performance of all preclinical treatments. The results showed that the synthesized complexes are potent for being active as antimicrobial, antioxidant, and anti-inflammatory prototypes. [ABSTRACT FROM AUTHOR]

This review summarizes developments in the synthesis and catalytic applications of those heterobimetallic carbene complexes in which at least two different metals are bound to the same ligand by at least one M-C(carbene) bond each. Several new synthetic methods for such complexes yielding well-defined and thoroughly characterized compounds are presented. The new complexes were found to be catalytically active in several (most often tandem) reactions. In certain cases, the incorporation of two different metals into the same imidazole- or triazol-based NHC-carbene complex resulted in the substantially higher catalytic activity of the heterobimetallic complex compared either to its homobimetallic analogs or to mixtures of comparable mononuclear complex fragments containing the two metals independently. This is a clear demonstration of advantageous metal–metal cooperation within the catalyst. Opposite examples are also discussed, where the heterobimetallic carbene complex proved inferior in relation to its homobimetallic analogs or to mixtures of homonuclear fragments. [ABSTRACT FROM AUTHOR]

The exploration for noble metals substitutes in catalysis has become a highly active area of research, driven by the pursuit of sustainable chemical processes. Although the utilization of base metals holds great potential as an alternative, their successful implementation in predictable catalytic processes necessitates the development of appropriate ligands. Such ligands must be capable of controlling their intricate redox chemistry and promote two-electron events, thus mimicking well-established organometallic processes in noble metal catalysis. While numerous approaches for infusing nobility to base metals have been explored, metal–ligand cooperation has garnered significant attention in recent years. Within this context, aluminium-based ligands offer interesting features to fine-tune the activity of metal centres, but their application in base metal catalysis remains largely unexplored. This perspective seeks to highlight the most recent breakthroughs in the reactivity of heterobimetallic aluminium–base-metal complexes, while also showcasing their potential to develop novel and predictable catalytic transformations. By turning the spotlight on such heterobimetallic species, we aim to inspire chemists to explore aluminium–base-metal species and expand the range of their applications as catalysts. [ABSTRACT FROM AUTHOR]

Although 2‐furyl‐carbenes (furfurylidenes) are prone to instantaneous electrocyclic ring opening, chiral [BiRh]‐paddlewheel complexes empowered by London dispersion allow (trifluoromethyl)furfurylidene metal complexes to be generated from a bench‐stable triftosylhydrazone precursor. These reactive intermediates engage in asymmetric [2+1] cycloadditions and hence open entry into valuable trifluoromethylated cyclopropane or ‐cyclopropene derivatives in optically active form, which are important building blocks for medicinal chemistry but difficult to make otherwise. [ABSTRACT FROM AUTHOR]