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DOI: 10.1039/A902061F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3289-3294

Orientational isomerism in bridging 2-pyridyl complexes: orthometallation of (S[hair space])-nicotine and (R)-1-(4-pyridyl)ethanol in triosmium clusters

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Antony J. Deeming, Marc J. Stchedroff, Caroline Whittaker, Alejandro J. Arce, Ysaura De Sanctis and Jonathan W. Steed

Abstract

Diastereomeric orthometallated products, formed by treating [Os3(CO)10(MeCN)2] with (S[hair space])-nicotine or (R[hair space])-1-(4-pyridyl)ethanol, have been partially separated by TLC but completely so by HPLC. The two diastereomers of [Os3(µ-H){µ-(R[hair space])-NC5H3CH(OH)Me-4}(CO)10] 1 and 2 and four isomers of [Os3(µ-H){µ-(S[hair space])-NC5H3C4H7NMe}(CO)10], 3 to 6, two diastereomers each for the products of metallation at the 2 and 6 positions respectively, have been separated and characterized by circular dichroism (CD) spectra to obtain their relative configurations. The CD spectra in the 230–500 nm wavelength range are totally characteristic of the configuration of the Os3CN group at atoms. A crystal structure determination for isomer 2 has allowed absolute configurations of all isomers to be established. There is little enantioselection in the orthometallation process and no detectable interconversion of isomers. The compound [Os3(µ-H)2{µ-(S[hair space])-NC5H3C4H7NMe}2(CO)8] was also obtained as a complex isomeric mixture which was not separated.

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