Reactions of [H2Os3(CO)10] with Conjugated Diynes (RC2C2R') Containing Nucleophilic Oxygen in 
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- 作者：Sergey P. Tunik ; Vassily D. Khripoun ; Irina A. Balova ; Maxim E. Borovitov ; Ivan N. Domnin ; Ebbe Nordlander ; Matti Haukka ; Tapani A. Pakkanen ; and David H. Farrar
- 刊名：Organometallics
- 出版年：2003
- 出版时间：August 18, 2003
- 年：2003
- 卷：22
- 期：17
- 页码：3455 - 3465
- 全文大小：235K
- 年卷期：v.22,no.17(August 18, 2003)
- ISSN：1520-6041
文摘
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 uponcoordination to the triosmium cluster, the nucleophilic oxygens of the R' substituents of 1and 2 take part in intramolecular cyclization reactions to give [HOs3(CO)10{
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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 thelatter compound, the furan moiety remains intact, but a carbonyl group dissociates fromthe 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 doesnot 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 startingcompounds has been used in the reaction of [H2Os3(CO)10] with HOCH2C2C2CH2OH in orderto investigate possible mechanisms of the cyclization reaction. The crystal and molecularstructures of clusters 5, 7, and 9 are presented.
-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 thelatter compound, the furan moiety remains intact, but a carbonyl group dissociates fromthe 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 doesnot 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 startingcompounds has been used in the reaction of [H2Os3(CO)10] with HOCH2C2C2CH2OH in orderto investigate possible mechanisms of the cyclization reaction. The crystal and molecularstructures of clusters 5, 7, and 9 are presented.