Advanced

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))

Tunik, S P; Khripun, V D; Balova, I A; Borovitov, M E; Domnin, I N; Nordlander, Ebbe LU ; Haukka, M; Pakkanen, T A and Farrar, D H (2003) In Organometallics 22(17). p.3455-3465
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.... (More)
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. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
22
issue
17
pages
3455 - 3465
publisher
The American Chemical Society
external identifiers
  • wos:000184751100020
  • scopus:0042378364
ISSN
1520-6041
DOI
10.1021/om0304107
language
English
LU publication?
yes
id
2c02b882-8ce8-41e9-bfad-7e597fb41901 (old id 128380)
date added to LUP
2007-07-09 14:23:22
date last changed
2018-05-29 11:21:46
@article{2c02b882-8ce8-41e9-bfad-7e597fb41901,
  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 Nordlander, Ebbe and Haukka, M and Pakkanen, T A and Farrar, D H},
  issn         = {1520-6041},
  language     = {eng},
  number       = {17},
  pages        = {3455--3465},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  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))},
  url          = {http://dx.doi.org/10.1021/om0304107},
  volume       = {22},
  year         = {2003},
}