Metal complexes with atropisomeric sulfur ligands in asymmetric hydroformylation X-ray structure of [Rh2(μ-biphes)(cod)2] (H2biphes = 4,4′-biphenanthrene-3,3′-dithiol)

The addition of the atropisomeric racemic sulfur compound 4,4′-biphenanthrene-3,3′-dithiol (H2 biphes) to a dichloromethane solution of [{M(μ-OMe)(cod)}2] (M = Rh, Ir, cod = cycloocta-1,5-diene) afforded the dithiolate-bridged complexes [{Rh2(μ-biphes)(cod)2}n] (n = 2 5 or n = 1 6) and [{Ir2(μ-biphes)(cod)2}n]·nCH2Cl27. When 1,1′-binaphthalene-2,2′-dithiol (H2 binas) reacted with [{Ir(μ-OMe)(cod)}2], complex [Ir2(μ-binas)(cod)2] 8 was obtained. Complexes 5 and 6 reacted with carbon monoxide to give the dinuclear tetracarbonyl complex [Rh2(μ-biphes)(CO)4] 9. The reaction of 9 with PR3 provided the mixed-ligand complexes [{Rh2(μ-biphes)(CO)2(PR3)2}2] · xCH2Cl2 (R = Ph, x = 2 10, C6H11, x = 1 11) and [{Rh2(μ-biphes)(CO)3(PR3)}2] · CH2Cl212 (R = OC6H4But-o). The crystal structure of 6 was determined by X-ray diffraction. Reaction of the dithioether ligand Me2biphes with [Rh(cod)2]ClO4 in CH2Cl2 solution afforded the cationic complex [Rh(cod)(Me2biphes)]ClO4 · CH2Cl213. Asymmetric hydroformylation of styrene was performed using the complexes described. The extent of aldehyde conversion ranges from 53 to 100%, with selectivities towards branched aldehydes in the range 51 to 96%. The enantioselectivities were quite low and did not exceed 20%.

Glastonbury Abbey: archaeological investigations 1904-79

This volume reports on the results of the Glastonbury Abbey Archaeological Archive Project, a collaboration between the University of Reading and the Trustees of Glastonbury Abbey, funded principally by the Arts and Humanities Research Council. The project has reassessed and reinterpreted all known archaeological records from the 1908–79 excavations and made the complete dataset available to the public through a digital archive hosted by the Archaeology Data Service (http://dx.doi.org/10.5284/1022585). The scope of the project has included the full analysis of the archaeological collections of Glastonbury Abbey by thirty-one leading specialists, including chemical and compositional analysis of glass and metal and petrological analysis of pottery and tile, and a comprehensive geophysical survey conducted by GSB Prospection Ltd. For the first time, it has been possible to achieve a framework of independent dating based on reassessment of the finds and radiocarbon dating of surviving organic material from the 1950s excavations. The principal aim of the Glastonbury Abbey Archaeological Project was to set aside previous assumptions based on the historical and legendary traditions and to provide a rigorous reassessment of the archive of antiquarian excavations. This research has revealed that some of the best known archaeological ‘facts’ about Glastonbury are themselves myths perpetuated by the abbey’s excavators.