PhD Project - [FSE Bicentenary PhD] Controlling magnetic relaxation times in rare earth single-molecule magnets and qubits at The University of Manchester, listed on FindAPhD.com

PhD Project - Sustainable Catalysis with Sb and Bi Pincer Complexes at The University of Manchester, listed on FindAPhD.com

We describe the synthesis of a phosphanyl-functionalized 1,3,5-triphosphabenzene that exhibits remarkably large indirect spin-spin coupling (432 Hz) between phosphorus-31 nuclei. The magnitude of this...

Arylxenonium(II) salts are the most numerous group of organoxenon compounds, i.e., those containing Xe–C bonds, and must be prepared by different routes that lack universality. Here, we present a general synthetic approach to arylxenonium(II) tetrafluoroborates [RXe][BF4] containing different degrees of fluorination at the aryl group R via processes that do not require the use of reactive gases or special equipment. The new synthetic access relies on the generation of aryldifluoroboranes RBF2 in dichloromethane solution by means of the reaction of K[RBF3] and BF3·OEt2, which are then transformed in a subsequent step to [RXe][BF4] salts. This route is not only more accessible than previously existing methods but also yields arylxenonium(II) tetrafluoroborates in higher yield and purity. Nevertheless, for highly acidic aryldifluoroborane species, namely those with R = C6F5, C6HF4, coordination of diethyl ether to the boron center prevents the transfer of the R group to the xenon atom. In these cases, a one-pot procedure starting from BR3, XeF2 and BF3·OEt2 enables their easy synthesis, including that of the novel compound [(2,3,5,6-C6HF4)Xe][BF4]. By means of the analysis of 11B NMR spectra of the aryldifluoroborane mixtures and theoretical calculations, the design of new organoxenonium(II) tetrafluoroborates through one route or the other can be tackled.

The paper introduces bimetallic Ir/Pd complexes as catalysts to initiate an N-methylation coupled with an aminocarbonylation in a one-pot approach, in order to advance the field of carboxyamide synthe...

Dezernat Personal: Personal

Single-molecule magnets (SMMs) based on dysprosocenium cations, [Dy(CpR)2]+ (CpR = substituted cyclopentadienyl), have set record effective energy barriers to magnetic reversal (Ueff) and temperatures...

We describe the synthesis and isolation of a phosphinidene telluride. This species acts as a versatile phosphinidene transfer reagent accompanied by the extrusion of elemental tellurium.

Bismuth radical chemistry has attracted increased interest in recent years. Here, we report a series of bismuth–manganese complexes that catalyze the intramolecular redox-neutral coupling of alkyl iod...

A series of cationic main-group complexes was obtained using the neutral, zwitterionic ligand IDP. The Lewis acidity of these complexes is explored by catalytic hydrophosphinations and halide additio...

The reactivity of the kinetically stabilized stannylene (MesTer)2Sn (1) (MesTer = –C6H3-2,6-(2,4,6-Me3-C6H2)2) toward N2O is revisited, yielding the terminal tin(IV) hydroxide 2 via formal intramolecular C(sp3)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)2 (3) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)2Sn (4). Compound 4 can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (6). Both 4 and 6 serve as suitable precursors for the synthesis of the heteroleptic s-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe3)2} (5).

Reduction of MnII precursors with bulky diamide ligands provided access to a complex with the longest known Mn–Mn bond and to a rare example of N2 activation at high-spin MnI centers. While some instr...

The reaction of a dihydro-dialane supported by a hybrid ligand (DNI) with organic azides yields structurally diverse aluminium species, including the first example of low oxidation state aluminium az...

Reductive amination is a challenging reaction in catalysis that often gives poor yield and selectivity. We present an ironcatalyzed approach of synthesizing amines through reduction of nitriles throu...

Chiffre CHEM-PHARM-15179