Reversible addition of CO to coordinatively unsaturated high-spin iron(II) complexes

Several new coordinatively unsaturated iron(II) complexes of the types [Fe(EN-iPr)X2] (E = P, S, Se; X = Cl, Br) and [Fe(ON-iPr)2X]X containing bidentate EN ligands based on N-(2-pyridinyl)aminophosphines as well as oxo, thio, and seleno derivatives thereof were prepared and characterized by NMR spectroscopy and X-ray crystallography. Mössbauer spectroscopy and magnetization studies confirmed their high-spin nature with magnetic moments very close to 4.9 μB, reflecting the expected four unpaired d-electrons in all these compounds. Stable low-spin carbonyl complexes of the types [Fe(PN-iPr)2(CO)X]X (X = Cl, Br) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2X2] (X = Br) were obtained by reacting cis-Fe(CO)4X2 with the stronger PN donor ligands, but not with the weaker EN donor ligands (E = O, S, Se). Furthermore, the reactivity of [Fe(PN-iPr)X2] toward CO was investigated by IR spectroscopy. Whereas at room temperature no reaction took place, at −50 °C [Fe(PN-iPr)X2] added readily CO to form, depending on the nature of X, the mono- and dicarbonyl complexes [Fe(PN-iPr)(X)2(CO)] (X = Cl) and [Fe(PN-iPr)(CO)2X2] (X = Cl, Br), respectively. In the case of X = Br, two isomeric dicarbonyl complexes, namely, cis-CO,trans-Br-[Fe(PN-iPr)(CO)2Br2] (major species) and cis-CO,cis-Br-[Fe(PN-iPr)(CO)2Br2] (minor species), are formed. The addition of CO to [Fe(PN-iPr)X2] was investigated in detail by means of DFT/B3LYP calculations. This study strongly supports the experimental findings that at low temperature two isomeric low-spin dicarbonyl complexes are formed. For kinetic reasons cis,trans-[Fe(PN-iPr)(CO)2Br2] releases CO at elevated temperature, re-forming [Fe(PN-iPr)Br2], while the corresponding cis,cis isomer is stable under these conditions.

Ensuring the right to the city: pro-poor housing, urban development and tenure legalization in São Paulo, Brazil

São Paulo is one of Latin America’s most modern and developed cities, yet around one-third of its 10 million inhabitants live in poor-quality housing in sub-standard settlements. This paper describes the response of the São Paulo municipal government that took office in 2001. Through its Secretariat of Housing and Urban Development, it designed a new policy framework with a strong emphasis on improving the quantity and quality of housing for low-income groups. Supported by new legislation, financial instruments and partnerships with the private sector, the mainstays of the new policy are integrated housing and urban development, modernization of the administrative system, and public participation in all decision-making and implementation processes. The programmes centre on upgrading and legalizing land tenure in informal settlements, and regeneration of the city centre. The new focus on valuing the investments that low-income groups have already made in their housing and settlements has proved to be more cost-effective than previous interventions, leading to improvements on an impressive scale.

Facile in situ copper(ii) mediated C–S bond activation transforming dithiocarbimate to carbamate and thiocarbamate generating Cu(ii) and Cu(i) complexes

Facile in situ Cu(II) mediated transformation of p-tolylsulfonyldithiocarbimate in conjunction with polypyridyl or phosphine ligands into corresponding carbamate and thiocarbamate led to the formation of new copper complexes with varying nuclearities and geometries, via C-S bond activation of the ligand within identical reaction systems.

Valuation 'accuracy' within the Right to Buy process

Based on surveys undertaken with local authorities and valuers who provide the valuations on which purchase prices for local authority houses under the Right to Buy are based, this paper reports on research which aims to establish the reasons for the differences between the initial valuations provided by the local authority valuers and those provided by the District Valuer on appeal. The paper reports on the reasons why tenants appeal the initial valuation and discusses issues of valuation accuracy, uncertainty and the different and imperfect data available to valuers employed by the organisations involved, as well as the factors within the valuation process, including the absence of any requirement to agree a value, which contribute to the different outcomes.