Monetary policy and banking supervision: coordination instead of separation. CEPS Policy Brief No. 286, 12 December 2012

Introduction. Following the June 2012 European Council decision to place the ‘Single Supervisory Mechanism’ (SSM) within the European Central Bank, the general presumption in the policy discussions has been that there should be ‘Chinese walls’ between the supervisory and monetary policy arms of the ECB. The current legislative proposal, in fact, is explicit on this account. On the contrary, however, this paper finds that there is no need to impose a strict separation between these two functions. The authors argue, in fact, that a strict separation of supervision and monetary policy is not even desirable during a financial crisis when the systemic stability of the financial system represents the biggest threat to a monetary policy that aims at price stability. In their view, the key problem hampering the ECB today is that it lacks detailed information on the state of health of the banking system, which is often highly confidential. Chinese walls would not solve this problem. Moreover, in light of the fact that the new, proposed Supervisory Board will be composed to a large extent of representatives of the same institutions that also dominate the Governing Council, the paper finds that it does not make sense to have Chinese walls between two boards with largely overlapping memberships. In addition, it recommends that some members of the Supervisory Boards should be “independents” in order to reduce the tendency of supervisors to unduly delay the recognition of losses.

Interaction of 2-(arylazo)phenols with rhodium. Usual coordination vs. C-H and C-C activation

Reaction of 2-(2'-hydroxyphenylazo)phenol with [Rh(PPh3)(3)Cl] in refluxing benzene in presence of triethylamine afforded a red complex in which the ligand is coordinated to rhodium as a tridentate O,N,O-donor. However, similar reaction of [Rh(PPh3)(3)Cl] with 2-(2'carboxyphenylazo)-4-methylphenol yielded two complexes, viz. a blue one and a green one. In both the complexes the ligand is coordinated as C,N,O-donor. However, in the blue complex orthometallation takes place from the ortho-carbon atom, which bears -COOH group via decarboxylation and in green one orthometallation occurs from the other ortho-carbon. Structures of all the three complexes were determined by X-ray crystallography. In all the three complexes rhodium is sharing the equatorial plane with the tridentate ligand and a chloride, and the two triphenylphosphines are axially disposed. All of the complexes show intense MLCT transitions in the visible region. Cyclic voltammetry on these complexes shows a Rh(III)-Rh(IV) oxidation on the positive side of SCE and a reduction of the coordinated azophenolate ligand on the negative side. (c) 2006 Elsevier B.V. All rights reserved.

Construction of coordination polymers of cadmium(II) with mixed hexamethylenetetramine and terephthalate or thiocyanate ligands

Three new polymeric complexes [Cd(hmt)(SCN)(2)(H2O)(2)](n) (1), [Cd-3(mu(2)-hmt)(2)(SCN)(6)(H2O)(2)](n) (2), and [Cd-2(hmt)(2)(tP)(2)(H2O)(6)](n) (3) [hmt = hexamethylenetetramine, tp = terephthalate] have been synthesized and characterized by single crystal X-ray diffraction. Both the compounds 1 and 2 are 1-D polymers where Cd units are linked by double end-to-end thiocyanate bridges but in 2 the chain is wider containing three cadmium atoms instead of one as found in 1. In both compounds the coordination environment around cadmium atom is distorted octahedral. Compound 3 is a three-dimensional polymer having water-filled microporous channels. Both tp and brut are mu(2)-bridged. One of the acid groups of tp is coordinated in chelating bidentate and the other in monodentate fashion. Half of its Cd atoms are hexa-coordinated and the rest are hepta-coordinated. Thermogravimetric analysis and X-ray diffraction study of 3 show that its framework remains intact upon removal of water molecules. The flexibility of coordination number around cadmium atoms (six or seven) probably plays an important role in establishing the rigidity of the framework. (C) 2003 Elsevier Ltd. All rights reserved.

Syntheses and crystal structures of two new coordination polymers of Cd(II) using organic spacer and inorganic-bridging ligands

Two new cadmium (II) complexes [Cd(hmt)(dca)(2)] (n) (1) and [Cd-3(hmt)(2)(SeCN)(6)(H2O)(2)] (n) (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN6 chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe2N3O and CdSe2N4 chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and (SeSe)-Se-... interaction are extended to 2D supramolecular architecture.

The coordination chemistry of 1,2,4-triazinyl bipyridines with lanthanide(III) elements - implications for the partitioning of americium(III)

It has been established that 6-(5,6-dialkyl-1,2,4-triazin-3-yl)-2,2'-bipyridines (R,hemi-BTPs) have properties which are intermediate between those of the terpyridines and the bis(1,2,4-triazin-3-yl)pyridines (BTPs). However, they resemble the terpyridines much more closely than the BTPs. It has been shown that Et, hemi-BTP when dissolved in TPH-a dodecane-like solvent-is a selective reagent for the separation of americium(III) from europium(III). Solution NMR in acetonitrile largely confirmed the crystallographic results. There was no evidence for a 1 : 3 complex cation, or for significant differences between metal(III)-N distances for the pyridine and 1,2,4-triazine rings. Intramolecular hydrogen bonding plays a crucial role in the formation of metal coordination spheres, which explains the differences between the terpyridyl, R,hemi-BTPs and the BTPs. Protonation of the R,hemi-BTPs facilitates a conformational change which is necessary for complexation.

Extraction and coordination studies of the unexplored bifunctional ligand carbamoyl methyl sulfoxide (CMSO) with uranium(VI) and cerium(III) nitrates. Synthesis and structures of [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)]

The bifunctional carbamoyl methyl sulfoxide ligands, PhCH2SOCH2CONHPh (L-1), PhCH2SOCH2CONHCH2Ph (L-2), (PhSOCH2CONPr2)-Pr-i (L-3), PhSOCH2CONBu2 (L-4), (PhSOCH2CONBu2)-Bu-i (L-5) and PhSOCH2CON(C8H17)(2) (L-6) have been synthesized and characterized by spectroscopic methods. The selected coordination chemistry of L-1, L-3, L-4 and L-5 with [UO2(NO3)(2)] and [Ce(NO3)(3)] has been evaluated. The structures of the compounds [UO2(NO3)(2)((PhSOCH2CONBu2)-Bu-i)] (10) and [Ce(NO3)(3)(PhSOCH2CONBu2)(2)] (12) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of ligand L-6 with U(VI), Pu(IV) and Am(III) in tracer level showed an appreciable extraction for U(VI) and Pu(IV) in up to 10 M HNO3 but not for Am(III). Thermal studies on compounds 8 and 10 in air revealed that the ligands can be destroyed completely on incineration. The electron spray mass spectra of compounds 8 and 10 in acetone show that extensive ligand distribution reactions occur in solution to give a mixture of products with ligand to metal ratios of 1 : 1 and 2 : 1. However, 10 retains its solid state structure in CH2Cl2.

Coordination and separation studies of the uranyl ion with iso-butyramide based ligands: Synthesis and structures of [UO2(NO3)(2)((C3H7CON)-C-i{(C4H9)-C-i}(2))(2)] and [UO2(C6H5COCHCOC6H5)(2)((C3H7CON)-C-i{(C3H7)-C-i}(2))]

The coordination chemistry of iso-butyramide based ligands such as: (C3H7CON)-C-i((C3H7)-C-i)(2), (C3H7CON)-C-i(C4H9)(2) and (C3H7CON)-C-i((C4H9)-C-i)(2) with [UO2(NO3)(2) center dot 6H(2)O], [UO2(OO)(2) center dot 2H(2)O] {where OO = C4H3SCOCHCCCF3 (TTA), C6H5COCHCOCF3 (BTA) and C6H5COCHCOC6H5 (DBM)), [Th(NO3)(4) center dot 6H(2)O] and [La(NO3)(3) center dot 6H(2)O] has been evaluated. Structures for the compounds [UO2(NO3)(2)CC3H7CON{(C4H9)-C-i}(2))(2)] and [UO2(C6H5COCHCOC6H5)(2)((C3H7CON)-C-i{(C3H7)-C-i)(2))] have been determined by single crystal X-ray diffraction methods. Preliminary separation studies from nitric acid medium using the amide (C3H7CON)-C-i((C4H9)-C-i)(2) with U(VI), Th(IV) and La(Ill) ions showed the selective precipitation of uranyl ion from the mixture. Thermal study of the compound [UO2(NO3)(2)((C3H7CON)-C-i((C4H9)-C-i)(2))(2)] in air revealed that the ligands can be destroyed completely on incineration. (C) 2008 Elsevier Ltd. All rights reserved.

Coordination and extraction studies of an unexplored bi-functional ligand, carbamoyl methyl pyrazole (CMPz) with uranium(VI), lanthanum(III) and cerium(III) nitrates

The bi-functional carbamoyl methyl pyrazole ligands, C5H7N2CH2CONBu2 (L-1), (C5H7N2CH2CONBu2)-Bu-i (L-2), C3H3N2CH2CONBu2 (L-3), (C3H3N2CH2CONBu2)-Bu-i (L-4) and C5H7N2CH2CON(C8H17)(2) (L-5) were synthesized and characterized by spectroscopic and elemental analysis methods. The selected coordination chemistry of L-1 to L-4 with [UO2(NO3)(2)center dot 6H(2)O], [La(NO3)(3)center dot 6H(2)O] and [Ce(NO3)(3)center dot 6H(2)O] has been evaluated. Structures for the compounds [UO2(NO3)(2) C5H7N2CH2CONBu2] (6) [UO2(NO3)(2) (C5H7N2CHCONBu2)-Bu-i] (7) and [Ce(NO3)(3){C(3)H(3)N(2)CH(2)CON(i)Bu2}(2)] (11) have been determined by single crystal X-ray diffraction methods. Preliminary extraction studies of the ligand L-5 with U(VI) and Pu(IV) in tracer level showed an appreciable extraction for U(VI) and Pu(TV) up to 10 M HNO3 but not for Am(III). Thermal studies of the compounds 6 and 7 in air revealed that the ligands can be destroyed completely on incineration. (c) 2007 Elsevier Ltd. All rights reserved.