Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2CH groups being orthogonal to this plane; 1 and 2 have the Rh–(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

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.