Intramolecular C−H Activation of a Bisphenolate(benzene)-Ligated Titanium Dibenzyl Complex. Competing Pathways Involving α-Hydrogen Abstraction and σ-Bond Metathesis

A titanium dibenzyl complex featuring a ligand with two phenolates linked by a benzene-1,3-diyl group was found to undergo thermal decomposition to give toluene and a cyclometalated dimeric complex. The thermal decomposition followed first-order kinetics and was studied at a number of temperatures to determine the activation parameters (ΔH‡ = 27.2(5) kcal/mol and ΔS‡ = −6.2(14) cal/(mol K)). Deuterated isotopologues were synthesized to measure the kinetic isotope effects. The complexes with deuterium in the benzyl methylene positions decomposed more slowly than the protio analogues. Isotopologues of toluene with multiple deuteration positions were observed in the product mixtures. These data are consistent with competing α-abstraction and σ-bond metathesis

Robotic Lepidoptery: Structural Characterization of (mostly) Unexpected Palladium Complexes Obtained from High-Throughput Catalyst Screening

In the course of a high-throughput search for optimal combinations of bidentate ligands with Pd(II) carboxylates to generate oxidation catalysts, we obtained and crystallographically characterized a number of crystalline products. While some combinations afforded the anticipated (L-L)Pd(OC(O)R)_2 structures (L-L = bipyridine, tmeda; R = CH_3, CF_3), many gave unusual oligometallic complexes resulting from reactions such as C−H activation (L-L = sparteine), P−C bond cleavage (L-L = 1,2-bis(diphenylphosphino)ethane, and C−C bond formation between solvent (acetone) and ligand (L-L = 1,4-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene). These findings illustrate potential pitfalls of screening procedures based on assuming uniform, in situ catalyst self-assembly

A systematic review of evidence for fitness-to-drive among people with the mental health conditions of schizophrenia, stress/anxiety disorder, depression, personality disorder and obsessive compulsive disorder

BACKGROUND: Limited evidence exists regarding fitness-to-drive for people with the mental health conditions of schizophrenia, stress/anxiety disorder, depression, personality disorder and obsessive compulsive disorder (herein simply referred to as 'mental health conditions'). The aim of this paper was to systematically search and classify all published studies regarding driving for this population, and then critically appraise papers addressing assessment of fitness-to-drive where the focus was not on the impact of medication on driving. METHODS: A systematic search of three databases (CINAHL, PSYCHINFO, EMBASE) was completed from inception to May 2016 to identify all articles on driving and mental health conditions. Papers meeting the eligibility criteria of including data relating to assessment of fitness-to-drive were critically appraised using the American Academy of Neurology and Centre for Evidence-Based Medicine protocols. RESULTS: A total of 58 articles met the inclusion criteria of driving among people with mental health conditions studied, and of these, 16 contained data and an explicit focus on assessment of fitness-to-drive. Assessment of fitness-to-drive was reported in three ways: 1) factors impacting on the ability to drive safely among people with mental health conditions, 2) capability and perception of health professionals assessing fitness-to-drive of people with mental health conditions, and 3) crash rates. The level of evidence of the published studies was low due to the absence of controls, and the inability to pool data from different diagnostic groups. Evidence supporting fitness-to-drive is conflicting. CONCLUSIONS: There is a relatively small literature in the area of driving with mental health conditions, and the overall quality of studies examining fitness-to-drive is low. Large-scale longitudinal studies with age-matched controls are urgently needed in order to determine the effects of different conditions on fitness-to-drive