Reactions of [H2Os3(CO)10] with Conjugated Diynes (RC2C2R‘) Containing Nucleophilic Oxygen in β Position of a Substituent (R = Ph, R‘ = CH2OH, C(O)Ph; R = R‘ = CMe2(OH))
| Autor: | Sergey P. Tunik, Ebbe Nordlander, I N Domnin, Tapani A. Pakkanen, Vassily D. Khripun, Irina A. Balova, Matti Haukka, David H. Farrar, M. E. Borovitov |
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| Rok vydání: | 2003 |
| Předmět: | |
| Zdroj: | Organometallics. 22:3455-3465 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om0304107 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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