The preparation and characterisation of rhodium(III) and Iridium(III) half sandwich complexes with napthalene-1,8-dithiolate, acenaphthene-5,6-dithiolate and biphenyl-2,2′-dithiolate

The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp*M(PEt3) (S-R-S)], M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (NaphthS2, a), acenaphthene-5,6-dithiolate (AcenapS2, b) and biphenyl-2,2′-dithiolate (BiphenS2, c) is reported. We also describe the isolation of a new compound acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spectroscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H2a), acenaphthene-1,8-dithiol (H2b), 1,1′-biphenyl-2,2′-dithiol (H2c) and benzene-1,2-dithiol (H2d) have also been characterised by single crystal X-ray diffraction.PostprintPeer reviewe

Mapping and characterization of structural variation in 17,795 human genomes

A key goal of whole-genome sequencing for studies of human genetics is to interrogate all forms of variation, including single-nucleotide variants, small insertion or deletion (indel) variants and structural variants. However, tools and resources for the study of structural variants have lagged behind those for smaller variants. Here we used a scalable pipeline1 to map and characterize structural variants in 17,795 deeply sequenced human genomes. We publicly release site-frequency data to create the largest, to our knowledge, whole-genome-sequencing-based structural variant resource so far. On average, individuals carry 2.9 rare structural variants that alter coding regions; these variants affect the dosage or structure of 4.2 genes and account for 4.0–11.2% of rare high-impact coding alleles. Using a computational model, we estimate that structural variants account for 17.2% of rare alleles genome-wide, with predicted deleterious effects that are equivalent to loss-of-function coding alleles; approximately 90% of such structural variants are noncoding deletions (mean 19.1 per genome). We report 158,991 ultra-rare structural variants and show that 2% of individuals carry ultra-rare megabase-scale structural variants, nearly half of which are balanced or complex rearrangements. Finally, we infer the dosage sensitivity of genes and noncoding elements, and reveal trends that relate to element class and conservation. This work will help to guide the analysis and interpretation of structural variants in the era of whole-genome sequencing

Hydrofluorination of alkynes catalysed by gold bifluorides

The ERC (Advanced Investigator Award FUNCAT and PoC award GOLDCAT), the EPSRC and Syngenta are gratefully acknowledged for support of this work. Umicore AG is acknowledged for their generous gift of auric acid. S.P.N. is a Royal Society Wolfson Research Merit Award holder.We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.Publisher PDFPeer reviewe

Six-coordinated Cd(II) centres as four- or six-connected nodes in coordination polymer networks containing bis(4-pyridyl)amine

The networks for 2 and 3 were 4-fold interpenetrated and isotopological. The reaction of CdSO4 with bpaH+ led to the formation of a two-dimensional (2D) hydrogen-bonded net (4). Complex 4 consisted of discrete six-coordinate mononuclear units linked into a 2D network by a number of different hydrogen-bonding interactions. The topological analysis of this network showed it to be reminiscent of a 2D diagonal section of an α-polonium network

Synthesis of homoleptic and heteroleptic bis-N-heterocylic carbene group 11 complexes

A straightforward synthetic route has been developed permitting the formation of homoleptic and heteroleptic bis-N-heterocyclic carbene metal complexes. The methodology has proven efficient for all group 11 members. These complexes are easily synthesized using [M(Cl)(NHC)] with different NHC salts in the presence of inexpensive bases such as sodium hydroxide. These systems were fully characterized and displayed high stability even in the presence of light

CCDC 2281787: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 2339543: Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures

CCDC 2181467 &:2181468 Experimental Crystal Structure Determination

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures