Pentacoordinated iridium( i )-cyclooctadiene complexes featuring a coumarin-functionalised imidazoline– or benzimidazoline–NHC ligand exhibit fluxional behavior as consequence of the hemilability pyrone ring in coumarin wingtip.

The efficient synthesis of two new stereoisomeric 3-aminocyclooctanetriols and their halocyclitol derivatives starting from cis,cis -1,3-cyclooctadiene are reported. Reduction cyclooctene endoperoxide, obtained by photooxygenation -1,3-cyclooctadiene, with zinc yielded a diol followed acetylation the hydroxy group, which gave dioldiacetate OsO 4 /NMO oxidation. cyclooctane prepared was converte...

Two synthetic strategies are investigated for the preparation of water-soluble iridium-based catalysts for NMR signal amplification by reversible exchange (SABRE). In one approach, PEGylation of a variant N-heterocyclic carbene provided a novel catalyst with excellent water solubility. However, while SABRE-active in ethanol solutions, the catalyst lost activity in >50% water. In a second approa...

The molybdenum-based monoaryloxide monopyrrolide (MAP) species, Mo(NAd)(CHCMe(2)Ph)(C(4)H(4)N)(HIPTO) (2a), which contains "small" imido (Ad = 1-adamantyl) and "large" aryloxide (HIPTO = O-2,6(2,4,6-i-Pr(3)C(6)H(2))C(6)H(3)) ligands, catalyzes Z-selective metathesis reactions as a consequence of intermediate metallacyclobutane species not being able to have an (anti) substituent pointing toward...

A pair of trans,trans-muconate ligands have been successfully aligned in two novel Au(I) macrocycles by design from phosphino metal precursors that undergo photochemical cycloaddition reactions quantitatively, resulting in the formation of cyclooctadiene derivatives.

The facile regioselective synthesis of the P(iii) substituted thiazol-2-thione 2 is presented. Reaction of 2 with hydrogenperoxide-urea, elemental sulfur and selenium resulted in P(v) chalcogenide thiazol-2-thiones 3-5. All compounds were characterized using (31)P, (1)H, (13)C NMR, IR and elemental analyses and, additionally, by the single-crystal X-ray diffraction technique. Oxidative desulfur...

Rhodium(I) complexes of the hybrid ylide-phosphine ligands, Ph2P(CH2)nPPh2(CHC(O)C6H5) (n = 1: dppm-yl, or 2: dppe-yl) have been synthesised from [Rh(μ-Cl)(COD)]2 (COD = 1,5-cyclooctadiene) and characterized by NMR spectroscopic and X-ray structural methods. The dppe-yl behaves as an ambidentate ligand; it functions as a monodentate P-donor ligand with a dangling ylidic carbon in the neutral ch...

The thermal conversion of cis-bicyclo[4.2.0]oct-7-ene to cis,cis-1,3-cyclooctadiene might involve a direct disrotatory ring opening, or it might possibly take place by way of cis,trans-1,3-cyclooctadiene. This cis,trans-diene might possibly form the more stable cis,cis isomer through a [1,5] hydrogen shift or a trans-to-cis isomerization about the trans double bond. Deuterium kinetic isotope ef...

The two highly flexible ligands 1,1'-bis(4-phospholanobutyl)ferrocene (5a) and 1,1'-bis(5-phospholanopentyl)ferrocene (5b) reacted with [PtCl2(cod)] (cod = 1,5-cyclooctadiene), [AuCl(tht)] (tht = tetrahydrothiophene) and [{RhCl(CO)2}2] to give the respective chelate complexes cis-[PtCl2(5a,b-κ(2)P,P')] (7a,b), [AuCl(5a,b-κ(2)P,P')] (8a,b) and trans-[RhCl(CO)(5b-κ(2)P,P')] (9b). Treatment of 5a,...