Primary dysfunction of the afferent limb of the arterial baroreceptor reflex system in a patient with severe supine hypertension and orthostatic hypotension

A 33 year old man with a history of recurrent episodes of orthostatic dizziness since adolescence was noted to have a supine blood pressure of 200/120 mm Hg and a standing blood pressure of 90/60 mm Hg. Results of extensive laboratory studies for secondary hypertension were negative. Studies of the autonomic nervous system function revealed normal plasma catecholamines, cold pressor test and response to 4 minute 30% of maximal static handgrip contraction and an appropriate increase in heart rate on intravenous injection of atropine. In contrast, the heart rate response to phenylephrine and sodium nitroprusside infusion, carotid massage and graded neck suction with an airtight chamber was very abnormal, indicating marked dysfunction of the afferent limb of the arterial baroreceptor reflex system. Methyldopa decreased the supine hypertension and increased the standing blood pressure

The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes

YesThe functionalisation of the 16-electron complex [Os(η6-p-cymene)(1,2-dicarba-closo-dodecarborane- 1,2-dithiolato)] (1) with a series of Lewis bases to give the 18-electron complexes of general formula [Os(η6-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)(L)] (L = pyridine (2), 4-dimethylaminopyridine (3), 4-cyanopyridine (4), 4-methoxypyridine (5), pyrazine (6), pyridazine (7), 4,4’-bipyridine (8) and triphenylphosphine (9)) is reported. All 18-electron complexes are in equilibrium in solution with the 16-electron precursor, and thermochromic properties are observed in some cases (2, 3, 5, 8, and 9). The binding constants and Gibbs free energies of the equilibria are determined using UV-visible titrations and their stabilities investigated. Synthetic routes for forcing the formation of the 18-electron species are proposed, and analytical methods to characterise the equilibria are described.We thank the Leverhulme Trust (Early Career Fellowship No. ECF-2013-414 to NPEB), and the University of Warwick (Grant No. RD14102 to NPEB)

Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands

YesHalf-sandwich metal complexes are of considerable interest in medicine, material, and nanomaterial chemistry. The design of libraries of such complexes with particular reactivity and properties is therefore a major quest. Here, we report the unique and peculiar reactivity of eight apparently 16-electron half-sandwich metal (ruthenium, osmium, rhodium, and iridium) complexes based on benzene-1,2-dithiolato and 3,6-dichlorobenzene-1,2-dithiolato chelating ligands. These electron-deficient complexes do not react with electron-donor pyridine derivatives, even with the strong σ-donor 4-dimethylaminopyridine (DMAP) ligand. The Ru, Rh, and Ir complexes accept electrons from the triphenylphosphine ligand (σ-donor, π-acceptor), whilst the Os complexes were found to be the first examples of non-electron-acceptor electron-deficient metal complexes. We rationalized these unique properties by a combination of experimental techniques and DFT/TDFT calculations. The synthetic versatility offered by this family of complexes, the low reactivity at the metal center, and the facile functionalization of the non-innocent benzene ligands is expected to allow the synthesis of libraries of pseudo electron-deficient half-sandwich complexes with unusual properties for a large range of applications