Reactions of [H2OS3(CO)(10)] with conjugated diynes (RC2C2R ') containing nucleophilic oxygen in beta position of a substituent (R = Ph, R ' = CH2OH, C(O)Ph; R = R ' = CMe2(OH))

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Bibtex

@article{2c02b8828ce841e9bfad7e597fb41901,
title = "Reactions of [H2OS3(CO)(10)] with conjugated diynes (RC2C2R ') containing nucleophilic oxygen in beta position of a substituent (R = Ph, R ' = CH2OH, C(O)Ph; R = R ' = CMe2(OH))",
abstract = "Reactions of [H2Os3(CO)10] with a series of diynes, RC2C2R' (1: R = Ph, R' = CH2OH; 2: R = Ph, R' = C(O)Ph; 3: R = R' = C(OH)Me2), have been studied. It was found that upon coordination to the triosmium cluster, the nucleophilic oxygens of the R' substituents of 1 and 2 take part in intramolecular cyclization reactions to give [HOs3(CO)10{-1:2-PhCH2(C=CH-C=CH-O)}] (5) and [HOs3(CO)10{-1:1-Ph(C=CH-C=C-O)CPh}] (6), respectively, both of which contain furan rings coordinated to the cluster core. On heating of the latter compound, the furan moiety remains intact, but a carbonyl group dissociates from the cluster, leading to the formation of [HOs3(CO)9(3-1:3:1-Ph(C=CH-C=C-O)CPh)] (7) with a closed {"}C3Os3{"} pentagonal pyramidal structure. Reaction of [H2Os3(CO)10] with 3 does not lead to cyclization of the diyne; instead, the clusters [Os3(CO)10{3-2-(RCH=CH-C2R)}] (8) and [Os3(CO)10{3-2-(RC2C2R)}] (9) are formed. Deuterium labeling of the starting compounds has been used in the reaction of [H2Os3(CO)10] with HOCH2C2C2CH2OH in order to investigate possible mechanisms of the cyclization reaction. The crystal and molecular structures of clusters 5, 7, and 9 are presented.",
author = "Tunik, {S P} and Khripun, {V D} and Balova, {I A} and Borovitov, {M E} and Domnin, {I N} and Ebbe Nordlander and M Haukka and Pakkanen, {T A} and Farrar, {D H}",
year = "2003",
doi = "10.1021/om0304107",
language = "English",
volume = "22",
pages = "3455--3465",
journal = "Organometallics",
issn = "1520-6041",
publisher = "The American Chemical Society (ACS)",
number = "17",

}