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Here, we report our initial investigations into the coordination chemistry of symmetric diacylated thiourea ligands ((RCONH) 2 CS) (R = Me, Et or Ph) acting as both mono and dianionic ligands with platinum(II), palladium(II) and gold(III) metal centres. Initial investigations were centred on mixed ligand bis(triphenylphosphine) (PPh 3 ) complexes which were prepared by reactions between cis -[PtCl 2 (PPh 3 ) 2 ] and (RCONH) 2 CS. A subsequent series of mixed ligand complexes from the diethyl-diacylthiourea ligand ((CH 2 CH 2 CONH) 2 CS) with [PtCl 2 (dppe)] (dppe = Ph 2 PCH 2 CH 2 PPh 2 ), [PdCl 2 (phen)] (phen = 1,10-phenanthroline), [AuCl 2 (anp)] (anp = cyclometallated 2-anilinopyridyl) and [PtCl 2 (COD)] (COD = 1,5-cyclooctadiene) were also prepared. The complexes were characterized by a combination of common techniques (MS, NMR and SC-XRD) which determined that the ligands coordinated to the metal centres in an unexpected S,N bidentate chelate manner in all instances. The complexes showed a small degree of aqueous instability as a result of hydrolysis. Computational techniques (NCI, EDA and HS) were used to analyse complexes whose solid state structure was able to be determined crystallographically. The presence of a chalcogen bond between the thiourea sulfur and acyl oxygen atoms was revealed which dominates the molecular structure. The cyclometallated 2-anilinopyridyl gold(III) complex 1f demonstrates intermolecular dimerism in the solid state. Hirshfeld surface analysis was used to determine the percentage contribution of inherent intermolecular interactions to crystal packing and the specific contacts responsible for spatial orientations in 1a, 1b, and 1f.

This article highlights the benefits of electronic-consultations and outlines steps for a primary care-centered approach to implementation. We include descriptions of traditional and electronic-consultation delivery models from the perspective of referring primary care provider. We describe five best practices for consultations regardless of modality, including clearly defined criteria that are best suited for electronic-consultation. Primary care teams must be equipped to explain the electronic-consultation process to the patient, including when and how results will be communicated. A successful electronic-consultation depends on clear questions and communication, flexibility in available data, a set-up that is easy-to-navigate and the ability to nimbly pivot if an alternative modality is needed. Electronic-consultation implementation may begin small with a single consult service and could include broader healthcare systems considerations including financial implications and service agreements. Based on increasing demand and increasing electronic-consultation familiarity and adoption, electronic-consultation will be a future necessity for primary care., Competing Interests: Declaration of conflicting interestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Some half-sandwich compounds with a variety of ligands and metal centres have shown promising anticancer activity. Herein we report a series of reactions between the sulfonylthiourea ligands p -TolSO 2 NHC(S)NHPh, EtSO 2 NHC(S)NHPh and CH 3 SO 2 NHC(S)NHPh and [(η 6 - p -cymene)RuCl 2 ] 2 , [(η 6 -arene)RuCl 2 (PR 3 )] (arene = benzene or p -cymene), [Cp*MCl 2 (PR 3 )] or [Cp*RhCl 2 ] 2 (M = Ir(III), Rh(III)), Cp* = η 5 -pentamethylcyclopentadienyl, PR 3 = triphenylphosphine (PPh 3 ), tris(2-cyanoethyl)phosphine (tcep) and 1,3,5-triaza-7-phosphaadamantane (pta) and their corresponding piano stool complexes. Single crystal X-ray diffraction structure determinations indicated that the resulting linkage isomer of the complex, i.e. , proximal (coordination via S,N (sulfonated) placing the sulfonyl group near the coordination sphere) or distal (coordination via S,N (non-sulfonated) , placing the sulfonyl group away from the coordination sphere), is directly related to the steric bulk around the metal centre. Proximal to distal isomerisation of the complex [(η 6 - p -cymene)Ru{ p -TolSO 2 NC(S)N(PPh 3 )}] (1aL1) was observed by 1 H and 31 P{ 1 H} NMR spectroscopy. DFT calculations suggested this to be the result of the conversion from the initially formed kinetically favourable to the thermodynamically favourable isomer. Computational investigation of non-covalent interactions using the reduced density gradient also revealed a chalcogen bond present between the thiourea sulfur and sulfonyl oxygen atoms of complex 1aLa. The in vitro antiproliferative activity of several complexes was determined against human cancer cells, which revealed a correlation between potency and lipophilic properties of the ancillary ligands for a series of Ru(II) p -cymene complexes.