Themed collection Multimetallic complexes: synthesis and applications

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

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

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

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

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

Trinuclear versus dinuclear heterodimetallic U^VO₂⁺⋯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.

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

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.

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.

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.

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.

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

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

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

The U^IV–Rh^I 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.

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

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.

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

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.

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

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

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

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.

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.

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

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.

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

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