Reactions of Diacetylene Ligands with Trinuclear Clusters; Cyclization of Diynes with beta-amino moieties on the surface of H2Os3(CO)10
(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)
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https://lup.lub.lu.se/record/959226
- author
- Tunik, Sergey ; Khripun, Valerii ; Balova, Irina ; Nordlander, Ebbe LU ; Haukka, Matti ; Pakkanen, Tapani and Raithby, Paul
- organization
- publishing date
- 2001
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Organometallics
- volume
- 20
- issue
- 18
- pages
- 3854 - 3863
- publisher
- The American Chemical Society (ACS)
- 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
- 2016-04-01 12:25:20
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- 2022-03-29 00:40:54
@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 (ACS)}},
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}},
doi = {{10.1021/om010400a}},
volume = {{20}},
year = {{2001}},
}