The novel ruthenaphosphaalkenyl complex [Ru{PCH(SiMe 3 )}Cl-(CO)(PPh 3 ) 2 ], prepared from [RuHCl(CO)(PPh 3 ) 3 ] and Me 3 SiCP, exhibits ambiphilic behavior, reacting at phosphorus with both nucleophiles and electrophiles. Its reaction with Li(pz′) or K[HB(pz′) 3 ] (pz′ = pz, pz*) affords [Ru{η 1 -N:η 2 -P,C-P(pz′)CH(SiMe 3 )}(CO)(PPh 3 ) 2 ], a rare example of a ruthenium(0) η 2phosphaalkene complex and the first example of a P-pyrazolylphosphaalkene. Conversely, reaction with the electrophilic PhHgCl leads to metalation at phosphorus, affording [Ru{η 1 -P(HgPh)CH(SiMe 3 )}Cl 2 (CO)(PPh 3 ) 2 ].

Thioether complexes of WECl4 and WECl3 (E = S, O) are prepared and characterised; the dinuclear [(WSCl4)2{iPrS(CH2)2SiPr}] is shown to be an effective single source precursor for low pressure CVD of WS2 thin films.

The novel complexes trans-[Ru(dppe)2(C≡CR)(C≡P)] (R = CO2Me, C6H4OMe), the first to incorporate cyaphide as part of a conjugated system, are obtained in facile manner. The electronic structure of these compounds is probed by X-ray, DFT and UV/Vis studies.

The electrodeposition of MoS2 from dichloromethane (CH2Cl2) using tetrabutylammonium tetrathiomolybdate ([NnBu4]2[MoS4]) as a single source precursor is presented. The electrodeposition of MoS2 from CH2Cl2 requires addition of a proton donor to the electrolyte and trimethylammonium chloride (Me3NHCl) was used for this purpose. Electrochemical Quartz Crystal Microbalance (EQCM) experiments have been employed for a detailed study of the electrochemical mechanism and to study the role of the proton donor. EQCM reveals cathodic electrodeposition of MoS2 and anodic deposition of MoS3 as well as an additional corrosion process where the deposited MoS3 strips back into solution. The electrodeposited MoS2 films are amorphous in nature. All the films were found to be homogeneous in composition across the electrode area and to be reproducible between experiments. Annealing of the as-deposited films under a sulfur atmosphere results in crystalline MoS2 as confirmed by energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy and X-ray diffraction. The deposited films were smooth and planar, as observed with scanning electron microscopy (SEM), indicating a layer-by-layer growth typical of transition metal dichalogenides.

Heterostructures involving two-dimensional (2D) transition metal dichalcogenides and other materials such as graphene have a strong potential to be the fundamental building block of many electronic and opto-electronic applications. The integration and scalable fabrication of such heterostructures is of essence in unleashing the potential of these materials in new technologies. For the first time, we demonstrate the growth of few-layer MoS2 films on graphene via non-aqueous electrodeposition. Through methods such as scanning and transmission electron microscopy, atomic force microscopy, Raman spectroscopy, energy and wavelength dispersive X-ray spectroscopies and X-ray photoelectron spectroscopy, we show that this deposition method can produce large-area MoS2 films with high quality and uniformity over graphene. We reveal the potential of these heterostructures by measuring the photo-induced current through the film. These results pave the way towards developing the electrodeposition method for the large-scale growth of heterostructures consisting of varying 2D materials for many applications.