Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP)
(2013) In European Journal of Inorganic Chemistry p.2447-2459- Abstract
- Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by... (More)
- Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N-oxide. The metastable cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable-temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid-state structures of [{Os3(CO)11}2(-PSP)] and [Os3(CO)10(-PSP)] are reported. (Less)
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https://lup.lub.lu.se/record/3843440
- author
- Persson, Roger LU ; Stchedroff, Marc ; Gobetto, Roberto ; Carrano, Carl J. ; Richmond, Michael G. ; Monari, Magda and Nordlander, Ebbe LU
- organization
- publishing date
- 2013
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Tridentate ligands, Cluster compounds, Osmium, P, S ligands, Isomerization
- in
- European Journal of Inorganic Chemistry
- issue
- 13
- pages
- 2447 - 2459
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- wos:000318167500020
- scopus:84876521287
- ISSN
- 1099-0682
- DOI
- 10.1002/ejic.201201403
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 8eb0633b-62ef-4bf0-911c-887f12d2796c (old id 3843440)
- date added to LUP
- 2016-04-01 10:14:50
- date last changed
- 2022-03-19 18:51:49
@article{8eb0633b-62ef-4bf0-911c-887f12d2796c,
abstract = {{Reaction of [Os3(CO)11(NCMe)] with bis-diphenylphosphanylethylene sulfide, {Ph2PCH2CH2}2S (PSP), leads to the formation of [Os3(CO)11(PSP)] and [{Os3(CO)11}2(-PSP)] in good yield. Similarly, treatment of [Os3(CO)10(NCMe)2] with PSP affords the cluster [Os3(CO)10(-PSP)], in which the two phosphanes of the PSP ligand coordinate to different osmium atoms of the same triosmium unit. Reaction of [Os3(CO)11(PSP)] with [Os3(CO)10(NCMe)2] yields the compound 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether moiety and one of the phosphane groups of the PSP ligand are coordinated equatorially to the {Os3(CO)10} subunit. The cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] is also formed when [Os3(CO)11(PSP)] is oxidatively decarbonylated by reaction with trimethylamine N-oxide. The metastable cluster 1,2-[{Os3(CO)11}(3-PSP){Os3(CO)10}] undergoes slow isomerisation at room temperature to form 1,1-[{Os3(CO)11}(3-PSP){Os3(CO)10}] in which the thioether and phosphane moieties coordinate in a chelating mode to one of the {Os3(CO)10} subunits with the thioether moiety in an axial position. The dynamic behaviour of these clusters has been investigated by variable-temperature 13C{1H} and 13P{1H} NMR spectroscopy. The solid-state structures of [{Os3(CO)11}2(-PSP)] and [Os3(CO)10(-PSP)] are reported.}},
author = {{Persson, Roger and Stchedroff, Marc and Gobetto, Roberto and Carrano, Carl J. and Richmond, Michael G. and Monari, Magda and Nordlander, Ebbe}},
issn = {{1099-0682}},
keywords = {{Tridentate ligands; Cluster compounds; Osmium; P; S ligands; Isomerization}},
language = {{eng}},
number = {{13}},
pages = {{2447--2459}},
publisher = {{John Wiley & Sons Inc.}},
series = {{European Journal of Inorganic Chemistry}},
title = {{Synthesis, Characterization, and Dynamic Behaviour of Triosmium Clusters Containing the Tridentate Ligand {Ph2PCH2CH2}2S (PSP)}},
url = {{http://dx.doi.org/10.1002/ejic.201201403}},
doi = {{10.1002/ejic.201201403}},
year = {{2013}},
}