2,4,6-Trimethylbenzyl chloride (α2-chloroisodurene)

The X-ray structure of the title compound has been determined and it is compared with those of other substituted benzyl chlorides reported previously. It has an atypically long CH2–Cl bond.Publisher PDFPeer reviewe

tert-Butyl carbazate (N-Boc-hydrazine)

The X-ray structure of the title compound has been determined for the first time. There are four independent molecules which form a repeat unit packed in the crystal in alternating pairs with orthogonal orientation and further joined into infinite chains by hydrogen bonding.Publisher PDFPeer reviewe

Thiophene-3-carbonyl chloride

The X-ray structure of the title compound has been determined for the first time. It shows the ring flip disorder common among thiophene-3-carbonyl derivatives and the occurrence of this phenomenon in the structures of such compounds is discussed.Publisher PDFPeer reviewe

Rigid biimidazole ancillary ligands as an avenue to bright deep blue cationic iridium(III) complexes

EZ-C acknowledges the University of St Andrews for financial support. Date of Acceptance: 03/06/2014Herein we report the synthesis and optoelectronic characterisation of three deep blue-emitting cationic iridium complexes, of the form [Ir(dFppy)2(N^N)]PF6, bearing biimidazole-type N^N ancillary ligands (dFppyH = 2-(2,4-difluorophenyl)pyridine). Complex 1 contains the parent biimidazole, biim, while 2 contains a dimethylated analog, dMebiim, and 3 contains an ortho-xylyl-tethered biimidzole, o-xylbiim. We explore a strategy of tethering the biimidazole in order to rigidify the complex and increase the photoluminescent quantum yield, culminating in deep blue (λmax: 457 nm in MeOH at 298 K) ligand-centered emission with a very high photoluminescent quantum yield of 68% and microsecond emission lifetime. Density functional theory calculations elucidate the origin of such disparate excited state kinetics across this series, especially in light of virtually identical optoelectronic properties observed for these compounds.PostprintPeer reviewe

Enantioselective NHC-catalyzed redox [2+2] cycloadditions with perfluoroketones; a route to fluorinated oxetanes

The authors thank the Royal Society for a University Research Fellowship (A.D.S.), and the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) ERC grant agreement no. 279850 (A.T.D.).The N-heterocyclic carbene (NHC) catalyzed redox formal [2+2] cycloaddition between α-aroyloxyaldehydes and perfluoroketones, followed by ring-opening in situ delivers a variety of perfluorinated β-hydroxycarbonyl compounds in good yield, and excellent diastereo- and enantioselectivity. Through a reductive work-up and subsequent cyclization, this protocol offers access to highly substituted fluorinated oxetanes in two steps and in high ee.PostprintPeer reviewe

Diethyl 2,5-dihydroxy-3,6-diiodoterephthalate

The title compound is characterised for the first time by the full range of spectroscopic methods and its X-ray structure shows hydrogen bonded stacks with iodine atoms aligned.Publisher PDFPeer reviewe

Variable dimensionality in 'hollow' hybrid tin iodide perovskites

We acknowledge support from the University of St Andrews and the Leverhulme trust (RPG-2018-065).Two ‘hollow’ B-site deficient perovskites, (TzH)11(H3PO2)Sn6I23 and (TzH)3Sn2I7 (TzH+ = 1,2,4-triazolium, H3PO2 = hypohosphorous acid), have been prepared. (TzH)11(H3PO2)Sn6I23 is the first example of a 2D layered structure of this type. Leaving the same reaction mixture for an extended time also affords the 3D derivative (TzH)3Sn2I7.Publisher PDFPeer reviewe

Preparation and organometallic complexes of the new unsymmetrical Ligand: Ph2PNHC6H4PPh2

Deprotonation of (2-diphenylphosphino)benzeneamine with BuLi followed by reaction with ClPPh2 in THF gave Ph2PNHC6H4PPh2 in good yields. The new unsymmetrical ligand has been incorporated into a number of complexes [[Rh(Ph2PNHC6H4PPh2)(cod)][ClO4] 2, RhCl2(eta(5)-C4Me5) (Ph2PNHC6H4PPh2-P-(N)) 3, [RhCl(eta(5)-C5Me5) (Ph2PNHC6H4PPh2-P(N)P)][Cl] 4, IrCl2(eta(5)-C5Me5) (Ph2PNHC6H4PPh2P(N)) 5, RuCl2(eta(6)-(MeC6H4Pr)-Pr-i) (Ph2PNHC6H4PPh2-P-(N)) 6, [RuCl(eta(6)-Me-(C6H4Pr)-Pr-i) (Ph2PNHC6H4PPh2-P-(N),P)][BF4] 7, RuCl2(eta(6)-C6Me6) (Ph2PNHC6H4PPh2-P-(N)) 8, [RuCl(eta(6)-C6Me6) (Ph2PNHC6H4PPh2-P-(N),P)][BF4] 9, RuCl2(eta(3):eta(3)-C10H16) (Ph2PNHC6H4PPh2-P-(N)) 10, OsCl2(eta(6)-(MeC6H4Pr)-Pr-i)(Ph2NHPC6H4PPh2-P-(N)) 11] to demonstrate its coordination behaviour as a monodentate or as a chelate ligand. The X-ray structures of for 5, 9 and 10 are reported. (C) 1999 Elsevier Science S.A. All rights reserved.PostprintPeer reviewe

The X-ray Structures of (R)-2,2'-Dimethyl-1,1'-binaphthyl and (±)-2-Bromomethyl-2'-dibromomethyl-1,1'-binaphthyl

We would like to thank the Engineering and Physical Sciences Research Council and CRITICAT Centre for Doctoral Training for financial support [Grant Code: EP/L016419/1].Molecular structures of (R)-2,2'-dimethyl-1,1'-binaphthyl [monoclinic, a = 11.24420 (11), b = 10.56190 (9), c = 13.27180 (13) Å, β = 90.7041 (9)º, space group P21] and (±)-2-bromomethyl-2'-dibromomethyl-1,1'-binaphthyl [triclinic, a = 9.4637 (14), b = 9.9721 (18), c = 9.9922 (19) Å, α = 100.093 (5), β = 97.141 (5), γ = 92.585 (4)º, space group P-1] are reported and compared with those of other simple 2,2'-disubstituted-1,1'-binaphthyls.PostprintPeer reviewe

Generation and hydrolysis of N-acyloxazolinium salts allowing regiospecific acylation of chiral amino alcohols

In an attempt to form 2-alkylidene-1,3-oxazolidines, chiral 2-oxazolines have been N-alkylated and N-acylated. Two new N-methyloxazolinium salts have been prepared and characterised but base treatment resulted in their decomposition. In contrast, attempts to isolate three N-benzoyloxazolinium salts gave the products of their ring hydrolysis: unsymmetrically diacylated amino alcohols whose structure was confirmed by x-ray diffraction in one case. Overall the method allows stepwise regiospecific N,O-diacylation of 1,2-amino alcohols.PostprintPeer reviewe