Advanced

Reactions of Diacetylene Ligands with Trinuclear Clusters; Cyclization of Diynes with beta-amino moieties on the surface of H2Os3(CO)10

Tunik, Sergey; Khripun, Valerii; Balova, Irina; Nordlander, Ebbe LU ; Haukka, Matti; Pakkanen, Tapani and Raithby, Paul (2001) In Organometallics 20(18). p.3854-3863
Abstract
Reactions of [H2Os3(CO)10] with the substituted diynes R-C2-C2-R' (1, R = Ph, R' = CH2NHPh; 2, R = Ph, R' = CH2NHCH2Ph; 3, R = R' = CH2NHPh) afford the clusters [HOs3(CO)10(L)] (L = {-1:2-PhCH2C(H)=C-C(H)=C-NPh} (4), {-1:2-PhCH2C(H)=C-C(H)=C-NCH2Ph} (5), and {-1:1-CH3CC=C-C(H)=C(H)-NPh} (6), which have been characterized by single-crystal X-ray diffraction analyses as well as by various spectroscopic methods. In clusters 4-6, the starting diynes 1-3 have been rearranged to form substituted pyrrolyl rings which bridge two osmium atoms in 1:2- (4, 5) or 1:1- (6) coordination modes depending on the nature of substituents in 1-3. A possible reaction pathway for the diyne cyclization reactions that yield 4-6 involves initial transfer of a... (More)
Reactions of [H2Os3(CO)10] with the substituted diynes R-C2-C2-R' (1, R = Ph, R' = CH2NHPh; 2, R = Ph, R' = CH2NHCH2Ph; 3, R = R' = CH2NHPh) afford the clusters [HOs3(CO)10(L)] (L = {-1:2-PhCH2C(H)=C-C(H)=C-NPh} (4), {-1:2-PhCH2C(H)=C-C(H)=C-NCH2Ph} (5), and {-1:1-CH3CC=C-C(H)=C(H)-NPh} (6), which have been characterized by single-crystal X-ray diffraction analyses as well as by various spectroscopic methods. In clusters 4-6, the starting diynes 1-3 have been rearranged to form substituted pyrrolyl rings which bridge two osmium atoms in 1:2- (4, 5) or 1:1- (6) coordination modes depending on the nature of substituents in 1-3. A possible reaction pathway for the diyne cyclization reactions that yield 4-6 involves initial transfer of a hydride onto a coordinated diyne followed by a series of 1,3-shifts and subsequent nucleophilic attack of the nitrogen on the third carbon atom of the diyne system to afford the five-membered pyrrolyl ring. Cluster 6 and its previously characterized furanyl analogue [HOs3(CO)10{-1:1-(OCHCHCC)-C-CH3)}] (7) undergo facile thermal transformation accompanied by the loss of a CO ligand to give the clusters [HOs3(CO)9{3,3-CH3CC=C-C(H)=C(H)-NPh}] (8) and [HOs3(CO)9{3,3-(OCH=CHC=CCCH3)}] (9). In both 8 and 9, single-crystal X-ray analysis revealed the presence of pentagonal pyramid cluster cores containing three osmium and three carbon atoms. (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
20
issue
18
pages
3854 - 3863
publisher
The American Chemical Society
external identifiers
  • scopus:0035802145
ISSN
1520-6041
DOI
10.1021/om010400a
language
English
LU publication?
yes
id
9a345dbe-bb55-4090-af82-424136618331 (old id 959226)
date added to LUP
2008-08-18 12:39:49
date last changed
2018-01-07 06:11:10
@article{9a345dbe-bb55-4090-af82-424136618331,
  abstract     = {Reactions of [H2Os3(CO)10] with the substituted diynes R-C2-C2-R' (1, R = Ph, R' = CH2NHPh; 2, R = Ph, R' = CH2NHCH2Ph; 3, R = R' = CH2NHPh) afford the clusters [HOs3(CO)10(L)] (L = {-1:2-PhCH2C(H)=C-C(H)=C-NPh} (4), {-1:2-PhCH2C(H)=C-C(H)=C-NCH2Ph} (5), and {-1:1-CH3CC=C-C(H)=C(H)-NPh} (6), which have been characterized by single-crystal X-ray diffraction analyses as well as by various spectroscopic methods. In clusters 4-6, the starting diynes 1-3 have been rearranged to form substituted pyrrolyl rings which bridge two osmium atoms in 1:2- (4, 5) or 1:1- (6) coordination modes depending on the nature of substituents in 1-3. A possible reaction pathway for the diyne cyclization reactions that yield 4-6 involves initial transfer of a hydride onto a coordinated diyne followed by a series of 1,3-shifts and subsequent nucleophilic attack of the nitrogen on the third carbon atom of the diyne system to afford the five-membered pyrrolyl ring. Cluster 6 and its previously characterized furanyl analogue [HOs3(CO)10{-1:1-(OCHCHCC)-C-CH3)}] (7) undergo facile thermal transformation accompanied by the loss of a CO ligand to give the clusters [HOs3(CO)9{3,3-CH3CC=C-C(H)=C(H)-NPh}] (8) and [HOs3(CO)9{3,3-(OCH=CHC=CCCH3)}] (9). In both 8 and 9, single-crystal X-ray analysis revealed the presence of pentagonal pyramid cluster cores containing three osmium and three carbon atoms.},
  author       = {Tunik, Sergey and Khripun, Valerii and Balova, Irina and Nordlander, Ebbe and Haukka, Matti and Pakkanen, Tapani and Raithby, Paul},
  issn         = {1520-6041},
  language     = {eng},
  number       = {18},
  pages        = {3854--3863},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Reactions of Diacetylene Ligands with Trinuclear Clusters; Cyclization of Diynes with beta-amino moieties on the surface of H2Os3(CO)10},
  url          = {http://dx.doi.org/10.1021/om010400a},
  volume       = {20},
  year         = {2001},
}