The interplay of secondary Hg⋯S, Hg⋯N and Hg⋯π bonding interactions in supramolecular structures of phenylmercury(ii) dithiocarbamates

Three new phenylmercury(II) and one mercury(II) dithiocarbamate complexes viz. PhHg S2CN(PyCH2) Bz (1), PhHg S2CN(PyCH2)CH3 (2), PhHg S2CN(Bz)CH3 (3), and [Hg (NCS2(PyCH2)Bz)(2)] (4) (Py = pyridine; Bz = benzyl) have been synthesized and characterized by elemental analyses, IR, electronic absorption, H-1 and C-13 NMR spectroscopy. The crystal structures of 1, 2 and 3 showed a linear S-Hg-C core at the centre of the molecule, in which the metal atom is bound to the sulfur atom of the dithiocarbamate ligand and a carbon atom of the aromatic ring. In contrast the crystal structure of 4 showed a linear S-Hg-S core at the Hg(II) centre of the molecule. Weak intermolecular Hg center dot center dot center dot N (Py) interactions link molecules into a linear chain in the case of 1, whereas chains of dimers are formed in 2 through intermolecular Hg center dot center dot center dot N (Py) and Hg center dot center dot center dot S interactions. 3 forms a conventional face-to-edge dimeric structure through intermolecular Hg center dot center dot center dot S secondary bonding and 4 forms a linear chain of dimers through face-to-face Hg center dot center dot center dot S secondary bonding. In order to elucidate the nature of these secondary bonding interactions and the electronic absorption spectra of the complexes, ab initio quantum chemical calculations at the MP2 level and density functional theory calculations were carried out for 1-3. Complexes 1 and 2 exhibited photoluminescent properties in the solid state as well as in the solution phase. Studies indicate that Hg center dot center dot center dot S interactions decrease and Hg center dot center dot center dot N interactions increase the chances of photoluminescence in the solid phase

Concessionary nature of public-private partnerships in Russia and Kazakhstan: a critical review

This article provides a critical overview of Public-Private Partnerships (PPPs) in Russia and Kazakhstan and examines the rationale underpinning such partnerships. The analysis discusses the reasons why governments in Russia and Kazakhstan focus principally on concessions as a form of PPP and goes on to provide a critical assessment of the key approaches and situational factors relating to concessions in these two countries. The article finds that external globalization impulses pressed Russia and Kazakhstan to align their policies and institutions with western orthodoxy and perceived international best practice. An ever-increasing emphasis on use of PPPs has been a key feature of this alignment. However, the governments of Russia and Kazakhstan have increasingly resorted to concessions as progress with the development and implementation of Western style PPP models has stalled. This article concludes that the governments of Russia and Kazakhstan have demonstrated an overly optimistic approach to PPP and as a result may have substantially understated their overall concessional risks and costs. Features of Russian and Kazakhstani PPP arrangements such as ambiguity in output specification and extensive reliance on government subsidies, combined with lack of expertise of private partners, may significantly decrease concession benefits.