Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/1/anie_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90585/2/3414_ftp.pd

Carbon(sp 3 )Fluorine Bond‐Forming Reductive Elimination from Palladium(IV) Complexes

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/1/ange_201107816_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/90520/2/3470_ftp.pd

Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, using the pincer compounds (C^N^C)AuR (R = C6F5, CH=CMe2, Me and p-C6H4X, where X = OMe, F, H, But, Cl, CF3, or NO2) as starting materials (C^N^C = 2,6-(4′-ButC6H3)2pyridine dianion). Protodeauration followed by addition of 1 equiv. SMe2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe2)]+. Upon addition of a second SMe2 pyridine is displaced, which triggers reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl) > k(aryl) >> k(C6F5) > k(Me). Vinyl-aryl coupling is particularly fast, 1.15 × 10–3 L mol–1 s–1 at 221 K, while both C6F5 and Me couplings encountered higher barriers for the C-C bond forming step. Using P(p-tol)3 in place of SMe2 greatly accelerates C–C couplings. Computational modelling shows that in the C^N bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. C-C bond formation is rate limiting. In the non-chelating case, reductive C(sp2)-C(sp2) elimination from three-coordinate cations [(Ar1)(Ar2)AuL]+ is almost barrierless, particularly if L = phosphine

Spirit, mind and body: the archaeology of monastic healing

Archaeology and material culture are used in this chapter to consider how monastic experience responded to illness, ageing and disability. The approach taken is influenced by the material study of religion, which interrogates how bodies and things engage to construct the sensory experience of religion, and by practice-based approaches in archaeology, which examine the active role of space and material culture in shaping religious agency and embodiment. The archaeology of monastic healing focuses on the full spectrum of healing technologies, from managing the body in order to prevent illness, through to the treatment of the sick and preparation of the corpse for burial

Blue carbon stock of the Bangladesh Sundarban mangroves: what could be the scenario after a century?

The total blue carbon stock of the Bangladesh Sundarban mangroves was evaluated and the probable future status after a century was predicted based on the recent trend of changes in the last 30 years and implementing a hybrid model of Markov Chain and Cellular automata. At present 36.24 Tg C and 54.95 Tg C are stored in the above-ground and below-ground compartments respectively resulting in total blue carbon stock of 91.19 Tg C. According to the prediction 15.88 Tg C would be lost from this region by the year 2115. The low saline species composition classes dominated mainly by Heritiera spp. accounts for the major portion of the carbon sock at present (45.60 Tg C), while the highly saline regions stores only 14.90 Tg C. The prediction shows that after a hundred years almost 22.42 Tg C would be lost from the low saline regions accompanied by an increase of 8.20 Tg C in the high saline regions dominated mainly by Excoecaria sp. and Avicennia spp. The net carbon loss would be due to both mangrove area loss (~ 510 km2) and change in species composition leading to 58.28 Tg of potential CO2 emission within the year 2115

In memoriam Branko Cividini

Branko Cividini (Samobor, 13. lipnja 1953. - Zagreb, 5. svibnja 2017.