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Themed collection Multimetallic complexes: synthesis and applications

28 items
Editorial

Multimetallic complexes: synthesis and applications

Welcome to this themed issue of Dalton Transactions entitled: ‘Multimetallic complexes: synthesis and applications’.

Graphical abstract: Multimetallic complexes: synthesis and applications
Perspective

One-dimensional complexes extended by unbridged metal–metal bonds based on a HOMO–LUMO interaction at the dz2 orbital between platinum and heterometal atoms

Crystal and electronic structures of seventeen heterometallic one-dimensional chain complexes are reviewed and discussed.

Graphical abstract: One-dimensional complexes extended by unbridged metal–metal bonds based on a HOMO–LUMO interaction at the dz2 orbital between platinum and heterometal atoms
From the themed collection: 2017 Frontier and Perspective articles
Communication

Ethylene polymerization catalyzed by bridging Ni/Zn heterobimetallics

The effect of proximal Zn halides on Ni-catalyzed ethylene polymerization is reported in this work.

Graphical abstract: Ethylene polymerization catalyzed by bridging Ni/Zn heterobimetallics
Communication

C4-Ferrocenylsilyl-bridged and -substituted N-heterocyclic carbenes: complexation of germanium chloride

C4-Ferrocenylsilyl-bridged and -substituted N-heterocyclic carbenes and their germanium chloride complexes have been prepared and characterized.

Graphical abstract: C4-Ferrocenylsilyl-bridged and -substituted N-heterocyclic carbenes: complexation of germanium chloride
Communication

Heterobimetallic complexes of palladium and platinum containing a redox-active W[SNS]2 metalloligand

Heterobimetallic W–Pd and W–Pt complexes have been prepared using the redox-active W(SNS)2 metalloligand.

Graphical abstract: Heterobimetallic complexes of palladium and platinum containing a redox-active W[SNS]2 metalloligand
Communication

Synthesis and SMM behaviour of trinuclear versus dinuclear 3d–5f uranyl(V)–cobalt(II) cation–cation complexes

Trinuclear versus dinuclear heterodimetallic UVO2+⋯Co2+ complexes were selectively assembled via a cation–cation interaction by tuning the ligand. The trimeric complex, exhibits magnetic exchange and slow relaxation providing the first example of a U–Co exchange-coupled SMM.

Graphical abstract: Synthesis and SMM behaviour of trinuclear versus dinuclear 3d–5f uranyl(v)–cobalt(ii) cation–cation complexes
Communication

Dinuclear oxidative addition reactions using an isostructural series of Ni2, Co2, and Fe2 complexes

Dinuclear oxidative additions at metal–metal bonds are facilitated by redox-active supporting ligands.

Graphical abstract: Dinuclear oxidative addition reactions using an isostructural series of Ni2, Co2, and Fe2 complexes
Paper

Mono- and polynuclear Ag(I) complexes of N-functionalized bis(diphenylphosphino)amine DPPA-type ligands: synthesis, solid-state structures and reactivity

DPPA-type ligands (Ph2P)2N(p-Z)C6H4 (Z = H, SMe, OMe) led to Ag(I) complexes of various nuclearities and an unexpected influence of the para-substituent Z is observed, including for CH2Cl2 activation.

Graphical abstract: Mono- and polynuclear Ag(i) complexes of N-functionalized bis(diphenylphosphino)amine DPPA-type ligands: synthesis, solid-state structures and reactivity
Paper

A study of asymmetrical mixed-valent Mo2–Mo2 complexes in the class III regime

With thiolated oxalato bridging ligands, three strongly coupled, asymmetrical Mo2 dimers have been studied. In these strongly mixed-valence systems, the charge is unevenly distributed and electron transfer between the two bridged Mo2 centers occurs, as indicated by the LMCT absorption and supported by the DFT calculations.

Graphical abstract: A study of asymmetrical mixed-valent Mo2–Mo2 complexes in the class III regime
Paper

Quasi-1D chains of dinickel lantern complexes and their magnetic properties

Four new quasi-1D Ni2 lantern chain complexes of the form [Ni2(SOCR)4(L)] were prepared with N,N′-donor bridging ligands pyrazine and DABCO.

Graphical abstract: Quasi-1D chains of dinickel lantern complexes and their magnetic properties
Paper

Monodentate phosphine substitution in [Pd(κ3-dppf)(PR3)][BF4]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) compounds

The synthesis and dissociative monodentate phosphine substitution of [Pd(κ3-dppf)(P(p-C6H4R)3)][BF4]2 compounds is presented. DFT calculations further examines the nature of the Fe–Pd interaction of the κ3-dppf ligand.

Graphical abstract: Monodentate phosphine substitution in [Pd(κ3-dppf)(PR3)][BF4]2 (dppf = 1,1′-bis(diphenylphosphino)ferrocene) compounds
Paper

Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes

Z-type complexes featuring Rh → Al and Rh → Ga interactions show distorted Rh centers and fluxionality on the NMR timescale.

Graphical abstract: Structure and dynamic NMR behavior of rhodium complexes supported by Lewis acidic group 13 metallatranes
Paper

Complexes of MN2S2·Fe(η5-C5R5)(CO) as platform for exploring cooperative heterobimetallic effects in HER electrocatalysis

Comparative study of bimetallic complexes with electronic modulations emphasizes reduction-induced hemi-lability as the key step for electrocatalytic proton reduction.

Graphical abstract: Complexes of MN2S2·Fe(η5-C5R5)(CO) as platform for exploring cooperative heterobimetallic effects in HER electrocatalysis
Open Access Paper

Modulation of the CO2 fixation in dinickel azacryptands

Different linker molecules within the dinickel azacryptand moiety show strong influence towards their CO2 coordination behaviour.

Graphical abstract: Modulation of the CO2 fixation in dinickel azacryptands
Open Access Paper

Uranium rhodium bonding in heterometallic complexes

The UIV–RhI intermetallic distances in the U2Rh2 complex (left, 2.7601(5) Å) and URh complex (right, 2.7630(5) Å) are very short and almost identical in the solid state even though solution electrochemistry suggests very different metal-based reduction processes.

Graphical abstract: Uranium rhodium bonding in heterometallic complexes
Paper

On the coordination non-innocence of antimony in nickel(II) complexes of the tetradentate (o-(Ph2P)C6H4)3Sb ligand

The coordination non-innocence of antimony toward Cl in ClNi(o-(Ph2P)C6H4)3SbCl results from both structural and electronic effects.

Graphical abstract: On the coordination non-innocence of antimony in nickel(ii) complexes of the tetradentate (o-(Ph2P)C6H4)3Sb ligand
Paper

Mixing Li and Cs in the reduction of corannulene for the assembly of a cesium-capped sandwich with a hexanuclear heterometallic core

In the first Li/Cs organometallic self-assembly, the tetrareduced corannulene decks are angled up to keep the highly-charged (Li3Cs3)6+ unit in between, with two external Cs+ ions capping the sandwich from outside.

Graphical abstract: Mixing Li and Cs in the reduction of corannulene for the assembly of a cesium-capped sandwich with a hexanuclear heterometallic core
Paper

The first examples of multiply bonded dirhenium(III,II) paramagnetic complexes containing nitrobenzoate ligands: spectroscopic, structural, cytotoxicity and computational studies

The synthesis and structural characterization of the hitherto unreported multiply bonded paramagnetic dirhenium(III,II) nitrobenzoate complexes have been reported.

Graphical abstract: The first examples of multiply bonded dirhenium(iii,ii) paramagnetic complexes containing nitrobenzoate ligands: spectroscopic, structural, cytotoxicity and computational studies
Paper

Contrasting the group 6 metal–metal bonding in sodium dichromate(II) and sodium dimolybdate(II) polymethyl complexes: synthetic, X-ray crystallographic and theoretical studies

Adding TMEDA to [M4Cr2Me8] (M = Li, Na) causes the Li complex to go mononuclear, whereas MeNa is extruded to give [Na3Cr2Me7] and a shortening of the Cr⋯Cr separation.

Graphical abstract: Contrasting the group 6 metal–metal bonding in sodium dichromate(ii) and sodium dimolybdate(ii) polymethyl complexes: synthetic, X-ray crystallographic and theoretical studies
Paper

Inter-ligand electronic coupling mediated through a dimetal bridge: dependence on metal ions and ancillary ligands

The metal–metal bond orbitals and the ancillary ligands influence inter-ligand charge transfer through the dimetal bridge.

Graphical abstract: Inter-ligand electronic coupling mediated through a dimetal bridge: dependence on metal ions and ancillary ligands
Paper

Heterometallic molecular precursors for a lithium–iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition

Heterometallic single-source precursors with the appropriate Li : Fe ratio were shown to yield the target LiFeO2 cathode material upon thermal decomposition.

Graphical abstract: Heterometallic molecular precursors for a lithium–iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition
Paper

Synthesis and characterisation of tetranuclear ruthenium polyhydrido clusters with pseudo-tetrahedral geometry

A series of tetranuclear ruthenium polyhydrido complexes with electric charges from +2 to 0 was synthesized.

Graphical abstract: Synthesis and characterisation of tetranuclear ruthenium polyhydrido clusters with pseudo-tetrahedral geometry
Paper

Divergent reactivity of a new dinuclear xanthene-bridged bis(iminopyridine) di-nickel complex with alkynes

A new di-nickel complex supported by a relatively flexible xanthene-bridged bis(iminopyridine) ligand is reported and its reactivity in alkyne cycloaddition is investigated.

Graphical abstract: Divergent reactivity of a new dinuclear xanthene-bridged bis(iminopyridine) di-nickel complex with alkynes
Paper

A base-free synthetic route to anti-bimetallic lanthanide pentalene complexes

Homobimetallic complexes of Yb, Eu and Sm bridged by a silylated pentalene ligand have been prepared and intermetallic communication studied by magnetic measurements and cyclic voltammetry.

Graphical abstract: A base-free synthetic route to anti-bimetallic lanthanide pentalene complexes
Paper

Anilinopyridinate-supported Ru2x+ (x = 5 or 6) paddlewheel complexes with labile axial ligands

Five new metal–metal bonded Ru2 amidinate compounds with labile axial ligands are presented and discussed.

Graphical abstract: Anilinopyridinate-supported Ru2x+ (x = 5 or 6) paddlewheel complexes with labile axial ligands
Paper

Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes

Mono-, di- and trimetallic derivatives of the cross-conjugated 3-methylene-penta-1,4-diyne moiety have been prepared, and studied by (spectro)electrochemical methods.

Graphical abstract: Sandwich and half-sandwich metal complexes derived from cross-conjugated 3-methylene-penta-1,4-diynes
Paper

Fundamental organometallic chemistry under bimetallic influence: driving β-hydride elimination and diverting migratory insertion at Cu and Ni

Bimetallic effects on stoichiometric β-hydride elimination and migratory insertion reactions were examined.

Graphical abstract: Fundamental organometallic chemistry under bimetallic influence: driving β-hydride elimination and diverting migratory insertion at Cu and Ni
Paper

The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties

A versatile bifunctional linker provides access to multimetallic assemblies with photophysical properties, which can be exploited to detect carbon monoxide.

Graphical abstract: The stepwise generation of multimetallic complexes based on a vinylbipyridine linkage and their photophysical properties
28 items

About this collection

This issue highlights emerging trends in the synthesis and applications of multimetallic complexes, including bi- and tri-metallic assemblies as well as larger well-defined metal clusters.It covers all aspects of the study of multimetallic complexes, including their synthesis, electronic structure, magnetic and redox properties, reactivity, catalytic applications, and relevance to enzymatic processes.

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