Multimetallic Permethylpentalene Hydride Complexes.

The synthesis and characterization of group 4 permethylpentalene (Pn* = CMe) hydride complexes are explored; in all cases, multimetallic hydride clusters were obtained. Group 4 lithium metal hydride clusters were obtained when reacting the metal dihalides with hydride transfer reagents such as LiAlH, and these species featured an unusual hexagonal bipyramidal structural motif. Only the zirconium analogue was found to undergo hydride exchange in the presence of deuterium.

Heterodinuclear Zn(II), Mg(II) or Co(III) with Na(I) Catalysts for Carbon Dioxide and Cyclohexene Oxide Ring Opening Copolymerizations.

A series heterodinuclear catalysts, operating without co-catalyst, show good performances for the ring opening copolymerization (ROCOP) of cyclohexene oxide and carbon dioxide. The complexes feature a macrocyclic ligand designed to coordinate metals such as Zn(II), Mg(II) or Co(III), in a Schiff base 'pocket', and Na(I) in a modified crown-ether binding 'pocket'. The 11 new catalysts are used to explore the influences of the metal combinations and ligand backbones over catalytic activity and selectivity.

CO activation by permethylpentalene amido zirconium complexes.

We report the synthesis and characterisation of new permethylpentalene zirconium bis(amido) and permethylpentalene zirconium cyclopentadienyl mono(amido) complexes, and their reactivity with carbon dioxide.

Reversible coordination of N and H to a homoleptic = 1/2 Fe(i) diphosphine complex in solution and the solid state.

The synthesis and characterisation of the = 1/2 Fe(i) complex [Fe(depe)][BArF4] ([][BArF4]), and the facile reversible binding of N and H in both solution and the solid state to form the adducts [·N] and [·H], are reported. Coordination of N in THF is thermodynamically favourable under ambient conditions (1 atm; Δ = -4.9(1) kcal mol), while heterogenous binding is more favourable for H than N by a factor of ∼300.

Control of Metal-Organic Framework Crystallization by Metastable Intermediate Pre-equilibrium Species.

There is an increasing amount of interest in metal-organic frameworks (MOFs) for a variety of applications, from gas sensing and separations to electronics and catalysis. However, the mechanisms by which they crystallize remain poorly understood. Herein, an important new insight into MOF formation is reported.

Time-Resolved In Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.

Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species.