Themed collection In Celebration of David Cole-Hamilton's Career in Chemistry

It has been my privilege and pleasure to have been a friend of David Cole-Hamilton over many years. This Editorial provides a review of his research contributions.

It is with the greatest of pleasure that we recognise David Cole-Hamilton's many accomplishments with this special Commemorative issue.

A short overview of synthetic methods using H₂O₂ and/or peroxidic species for the elaboration of discrete or zero-dimensional species, as well as mono-, bi- and tri-dimensional materials is presented.

The use of single-source molecular precursors for lead chalcogenide thin films by CVD or as nanoparticles by solution methods is reviewed.

A safe and readily accessible method for the aerobic catalytic synthesis of nitriles from aldehydes or alcohols.

The cyclic peptide gramicidin S was used as a template for the construction of novel peptide-based bisphosphine ligands for asymmetric transition metal catalysis.

The f-block complexes ([M(L)(N{SiMe₃}₂)₂] L = bidentate alkoxy-tethered NHC ligand) with CO and CO₂, COS and N₂CPh₂ show to [M(L)₂(N{SiMe₃}₂)], show much more varied insertion chemistry than [M(N{SiMe₃}₂)₃].

The trimethylsilylethynyl moiety, –CCSiMe₃, is shown to act as an effective contact in Au|molecule|Au junctions.

The combination of Jahn–Teller distortion and chelating ligands produces a fine balance between competing coordination modes in manganese(III) resulting in well-ordered co-crystallization of two distinct assemblies from one set of components under a single set of conditions.

Nickel(II) complexes bearing a phosphine–sulfonate ligand, [(R₂PC₆H₄SO₃)NiMe(2,6-lutidine)] (R = cyclohexyl, 2-MeOC₆H₄, and 2-[2′,6′-(MeO)₂C₆H₃]C₆H₄, were synthesized and applied as catalysts for the cooligomerizations of ethylene and allyl monomers.

Polymer-supported PdNPs: from batch to continuous synthesis of fine chemicals.

The synthesis of stable imine (N^C)-cyclometallated ruthenium(II) complexes via C–H bond activation/deprotonation is described from the reaction of [RuCl₂(p-cymene)]₂, arylimines and KOAc in methanol at r.t.

Several active catalysts have been identified and applied in the hydrogenation of aromatic esters at temperatures as low as 30 °C.

The synthesis and characterization of a new class of cationic (NHC)gold(I) (NHC = N-Heterocyclic carbene) complexes containing the phosphate counterions TRISPHAT and TRISPHAT-N have been achieved.

Mesoporous silica nanobamboo with highly dispersed WC nanoparticles was synthesized by tuning the interaction between ammonium metatungstate and cetyltrimethylammonium bromide micelles.

New procedures for the synthesis of [Au(NHC)(OH)] are reported.

The unexpected reactivity towards water of an iridium acetyl complex points towards alternative by-product formation pathways in Ir-catalysed methanol carbonylation.

Sr_1−xNbO₃ is an unusual material that displays both metallic type conduction and photocatalytic activity, despite being an NbIV oxide, and it sustains photo-oxidation without degradation.

Unusual polarization of the Rh/O fragment of a (pincer)RhO molecule gives high reactivity towards the varied reagents CO, CO₂, and H₂.

This article shows that Ni₃(BTP)₂ adopts a low spin configuration which does not interact strongly with CO, CO₂, or H₂.

Under dihydrogen pressure, the pyridyl moiety of 2-(diphenylphosphino)pyridine can act as an internal base to assist the heterolytic cleavage of dihydrogen of platinum phosphine complexes.

This article describes a new strategy for the recycling of a homogeneous hydroformylation catalyst, by selective adsorption of the catalyst to tailor-made supports after a batchwise reaction.

The molecular structure of antimony(III) oxide has been re-investigated utilising a new high-temperature nozzle system designed for the Canterbury (NZ) gas electron diffraction apparatus.

The reversible regioselective methylation of a ruthenium polypyridyl complex bearing both a 1,2,4-triazolato and a pyrazine moiety is reported.

Ru(II) complexes bearing the polydentate ligands triphos and NP3 catalyse the dehydrogenation of formic acid to carbon dioxide and hydrogen at 80 °C in the presence of n-octyldimethylamine.

Iron(II) and cobalt(II) complexes of seven different terpyridine analogues containing diazinyl or triazinyl heterocyclic donors have been prepared. The electrochemical properties of the complexes depend particularly strongly on the nitrogen content of the ligands.

Scandium NMR and XAFS studies of the reaction of [ScCl₃(L₃)] (L₃ = R₃-tacn and R-SNS tridentate ligands) show that MeLi causes methylation at Sc, whereas AlMe₃ forms Sc–Cl–Al bridges.

Mes*₂P(O)Cl is a highly sterically crowded compound whose reduction requires very harsh conditions. Resulting secondary phosphine (Mes*)(2,4-tBu₂C₆H₃)PH is also very sterically encumbered. Synthetic and computational studies of this and other related crowded phosphorus species are reported.

Pore-flow-through silica monoliths featuring a bimodal distribution of macropores (4 μm) and mesopores (11 nm) loaded with 6 nm Pd nanoparticles demonstrate remarkable stability of the activity for the continuous selective hydrogenation of 1,5-cyclooctadiene and 3-hexyn-1-ol.

The phosphane-free catalytic system containing Pd(OAc)₂ and chiral ionic liquids containing L-prolinate and L-lactate anions and non-chiral quaternary ammonium cations efficiently catalyzed regio- and stereoselective Heck arylation of 2,3-dihydrofuran with aryl iodides. Excellent enantioselectivity (>99% ee) was obtained in the reaction with tetrabutylammonium L-prolinate.

The Si–H bonds of alkyl- aryl-substituted silanes have been functionalized using a silver-based catalyst for the carbene transfer reaction from diazocompounds.

Cyclometalated iridium complexes are catalytically active and can be easily accessed.

The formation of 16-electron ruthenium complexes via the loss of CO – an insight based on the potential energy profiles.

Governed by the pH and pressure, hydrogenation of [{RuCl₂(mtppms)₂}₂] yields various classical and non-classical Ru(II)-hydrides exhibiting different catalytic properties in hydrogenation of unsaturated aldehydes.

Diphenylphosphinobutane (dppb) stabilized bimetallic RuPt nanoparticles were prepared by co-decomposition of [Ru(COD)(COT)] and [Pt(CH₃)₂(COD)] organometallic precursors under mild conditions and in the presence of dppb.

The cis-[RuCl₂(κ²-P–P′)₂] complex containing the phospholyl(phosphino)methane ligand evolves very slowly at 20 °C into the trans-isomer, through decoordination of a phosphole arm.

o-Diphosphinotoluenes produce Pd-catalysts for methoxycarbonylation of ethene with activities ranging from zero to the highest reported to date.

Chalcogen silver bonding leads to a range of coordination polymers depending on the nature of the chalcogen and the counterion.

An inversion of natural regioselectivity in the Rh-catalyzed hydroformylation of styrene to the linear product by introducing electron-withdrawing ligands.

The successful application of catalytic chain transfer polymerisation (CCTP) by adopting an ‘in situ’ catalyst preparation methodology in several polymerisation media is described.

Various simple tris-cyclometallated Ir(III) complexes are efficient second-order NLO chromophores with a response tunable by an appropriate substitution of 2-phenylpyridine ligands.

A new catalyst composed of Pd nanoparticles supported on MgO is efficient for the regioselective hydrogenation of quinolines, a variety of alkenes representative of fuel components, and the partial saturation of biodiesel.

The synthesis and migratory insertion reactions of σ-monoalkyl phosphinito-imine Ni and Pd complexes stabilized by a solvent molecule or intramolecular π-interactions are reported.

The effect of β-diketonate co-ligands on the mesomorphism and photophysics of some di(alkoxyphenyl)pyridine complexes of platinum(II) is investigated.

A comparative study on the catalyzed hydrogenation of linear three-ring aromatic hydrocarbons and their N-heteroaromatic analogues by ruthenium complexes is reported, with a specific focus on the influence of methyl substituents attached to the “external” and “internal” rings of the substrates.

A diolefin Rh(I) amido catalyst converts efficiently a mixture of alcohols and nitrosoarenes to aldehydes and azoxyarenes.

N-Heterocyclic carbene coordination of some polypyridines has been demonstrated.

Macrocycles that combine pyrrole-imine and amine ether donor compartments form Ti, V, Cr, Co, and Pd complexes that adopt Pacman structures that facilitate the in-cleft binding of water through coordination and hydrogen bonds.

Preparation and characterization of water-soluble Rh(I) metallodendrimers. Hydroformylation under aqueous biphasic conditions is achieved at mild temperature and pressure. Good activities and selectivities are exhibited.

Activity and selectivity of NP catalysts with size under 3 nm could be controlled by the σ-donor π-acceptor ligands as with a homogeneous catalyst.

Colloidal nanocrystal quantum dots with a band gap in the near infra-red have potential application as the emitters for telecommunications or in vivo imaging, or as the photo-absorbing species in next generation solar cells or photodetectors.

Monodentate phosphine-functionalized phosphonium ionic liquids (PFILs) were employed as ligands for Rh complexes and used in the hydroformylation of higher alkenes.

Strategies for reducing the side-reactions of chemoenzymatic DKR: tuning the organometallic catalyst and entrapping the biocatalyst.

Rhodium(0) nanoparticles stabilized by a water-soluble polymer catalyzed aqueous hydrogenation reaction.

The platinum dinuclear complexes, cis-[Pt₂(μ-NHC)(dmso)₂Cl₄], of ditopic chiral carbene ligands are reported. ¹H, ¹³C, ¹⁹⁵Pt and ¹H–¹⁵N HMBC NMR data reveal the presence of rotamers in solution, arising from restricted rotation about the Pt–NHC bond.

A series of novel imidazolium, ammonium, phosphonium and pyridinium based salts with [closo-B₁₂Cl₁₂]²⁻ dianion were synthesized by straight forward metathetic reactions and characterized by physical methods.

A series of palladium(0) complexes bearing mixed phosphine/N-heterocyclic carbene supporting ligands are examined in aerobic oxidation of alcohols. These turn out to perform exceedingly well at low catalysts loadings under very mild conditions.

Diverse coordination modes are exhibited by the novel anionic amidinato NHC ligands.

The first organometallic and phosphine-based palladium complexes bearing NHC·CS₂ ligands have been prepared in good yield. Low loadings of selected complexes were found to be highly active and selective pre-catalysts for oxidative C–H functionalisation.

An innately chiral diphosphine ligand with a central amidinium group shows variable coordination ranging from μ-bridging and κ²-binding through solely the phosphines to a κ³-mode upon release of the NHC donor with base. Conformational isomerism is observed in the complexes containing the tridentate ligand bound to Rh(I), Pd(II) and Pt(II).

The title compounds shows interesting excited state charge delocalization and dynamics in S₁ and T₁ states as examined using fs and ns time-resolved UV-Vis and IR spectroscopy.

Three new 10-vertex rhodathiaboranes are sequentially formed in the reaction between [arachno-4-SB₈H₁₁]⁻ and [RhCl(PPh₃)₃]. This stepwise reactivity and the resulting closo → arachno → closo structural and electronic response augurs a rich chemistry.

Compounds [RhCl(diene)(P,SR)] with chiral ferrocenyl phosphine–thioethers ligands preferentially adopt a neutral square planar structure with a dangling thioether as shown by a combination of ¹H NMR, IR and DFT studies.

Two new complexes with linear Eu₄Cu₂ or Eu₄Ni₂ cores are formed with a salen type Schiff base which caps each end of the metal chain.

Oxidation of d⁶ W(P^HNP)(CO)₃ gives a full series of cationic and neutral tungsten(II) hydridocarbonyls and halocarbonyls.

Backbone reactivity of a bidentate PN-ligand in the context of N–H activation leads to Pd^II and Cu^I amido complexes.

A systematic study of Te(IV) halide chemistry (halide = F, Cl or Br) with soft, neutral thio-, seleno- and telluroether ligands reveals significant coordination chemistry with the TeX₄ Lewis acids, with clear boundaries between complexation and redox processes; NMR spectroscopic trends are reported and the distorted square pyramidal [TeF₄(OPR₃)] (R = Me or Ph) are included.

Reduction and subsequent metallation of the tethered carborane shown affords both 4,1,2- and 4,1,6- MC₂B-₁₀ metallacarboranes by two quite separate routes.

In the presence of Ru(H)₂(CO)(PPh₃)(xantphos), under N₂ or Ar, the alcohol function in lignin models is dehydrogenated. The ketone then undergoes C–O cleavage to form guaiacol and acetophenone derivatives; this hydrogenolysis also occurs readily under H₂. When a –CH₂– of the ketone is replaced by –CH(CH₂OH)–, the catalysed hydrogenolysis is inhibited due to formation of characterised inactive Ru species.

The 128.8 MHz ¹⁹⁵Pt NMR peaks of [Pt^35/37Cl_n(H₂^16/18O)_6−n]ⁿ⁻² (n = 2–6) complexes display unique ^35/37Cl and ^16/18O isotope resolved ‘fingerprints’ characteristic of the structure of the Pt^IV complexes, providing a novel method for unambiguous chemical speciation, particularly of the stereoisomers.