The crystal structure of the bicyclic hexaamine complex [Cu(fac-Me5-tricosane-N6)](ClO4)2.H2O (fac-Me5-tricosane-N6 = facial-1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosane) at 100 K defines an apparently tetragonally compressed octahedral geometry, which is attributed to a combination of dynamic interconversion and static disorder between two tetragonally elongated struc...

The base-free dimethyl scandium complex supported by the bulky beta-diketiminato ligand ArNC((t)Bu)CHC((t)Bu)NAr (Ar = 2,6-(i)Pr(2)C(6)H(3), 1) reacts with various equivalencies of the strong organometallic Lewis acid B(C(6)F(5))(3) to give scandium alkyl cations. With 0.5 equiv, a monocationic mu-methyl dimer (2) was observed spectroscopically. Reaction with a further 0.5 equiv of borane gives...

Reaction of PH,Ph with CpzMoz(CO), (M-MO) results in sequential formation of cp,Mo,(CO),(PHzPh)z and fluxional Cp,Mo,(p-HXP-PHPhXCO&. Proton abstraction from Cp,Mo,(p-HXF-PHPhXC0)4 affords [Cp,Mo,(p-PHPhXCO),lwhile reaction with [Ph$Z’F~l yields fluxional Cp,Mo&HXF-PFPhXCO)g.

We have evaluated the role of achiral pyrazolidinone templates in conjunction with chiral Lewis acids in room temperature, enantioselective Diels-Alder cycloadditions. The role of the fluxional N(1) substituent was examined, with the bulky 1-naphthylmethyl group providing enantioselectivities up to 99% ee, while templates with smaller fluxional groups gave lower selectivities. High selectivitie...

In this paper we have prepared a series of Ti(iv), Hf(iv) and Al(iii) complexes based on bipyrrolidine salan pro-ligands. The Hf(iv) complexes have all been characterised in the solid-state, the chiral ligands coordinate to Hf(iv) in an α-cis manner whereas the meso ligand coordinates in a β-cis geometry. The Hf(iv) complexes are all active for the ROP of rac-lactide in the melt, with the fluxi...

The fluxional barrier of (dicarbonyl)[dihydrobis(3,5-dimethylpyrazol-1-yl)borato][eta-(1,2,3)-2-methylpropen-1-yl]-molybdenum (1) has been measured and a complete assignment of its (1)H, (13)C and (15)N NMR signals has been carried out. Theoretical calculations at the B3LYP/LANL2DZ level including GIAO absolute shieldings (sigma) have allowed to analyze the molecular contributions to the barrie...

The temperature-dependent ‘H and 13C NMR spect_ra of (hS-C.r.~Hs)3Rh3 (CO)C6H&sC6Hs support the view that this molecule is fluxional in solution at room temperature but is in a frozen conformation at -88”; NMR data of (h’-CsHs)sRh3 (CO) CeFsCsC6F5 indicate that this molecule appears to be static at room temperature and fluxional at elevated temperatures. The NMR data are consistent with structu...

A redox-active, tetradentate ligand, N,N'-bis-(3-dimethylamino-propyl)-4,5-dimethoxy-benzene-1,2-diamide ([N(2)N(2)(cat)](2-)), was developed, and the six-coordinate metal complexes [N(2)N(2)(cat)]TiCl(2) (3) and [N(2)N(2)(cat)]ZrCl(2) (4) were synthesized. The tetradentate ligand was determined to be fluxional in 3 and 4, enabled by reversible dissociation of the neutral amine groups of the [N...

Dipolar addition of cyclic azomethine imines with cyclic vinyl sulfones gave rise to functionalized tricycles that exhibited fluxional behavior in solution at room temperature. The scope of the synthetic methodology was explored, and the origin of the fluxional behavior was probed by NMR methods together with DFT calculations. This behavior was ultimately attributed to stereochemical inversion ...

The technique of velocity modulation spectroscopy has recently been combined with cavity enhancement and frequency modulation methods into a technique called noise-immune cavity-enhanced optical heterodyne velocity modulation spectroscopy (NICE-OHVMS). We have implemented NICE-OHVMS with a cw-optical parametric oscillator (OPO) tunable from 3.2 to 3.9 lm, and used it to record spectra of the R(...