Chiral hexarhodium clusters containing heterobidentate phosphine ligands, a structural and reactivity study
(2003) In Dalton Transactions p.2457-2467- Abstract
- Some intrinsically chiral [Rh6(CO)14(µ,2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16–x(NCMe)x](x= 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x= 1 the initial products are the clusters [Rh6(CO)15(1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(µ,2-PX)]. The structures of the [Rh6(CO)15(1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve... (More)
- Some intrinsically chiral [Rh6(CO)14(µ,2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16–x(NCMe)x](x= 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x= 1 the initial products are the clusters [Rh6(CO)15(1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(µ,2-PX)]. The structures of the [Rh6(CO)15(1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve phosphorus atom coordination to a rhodium atom. In addition, the solid state structures of the [Rh6(CO)14(µ,2-Ph2P(2-benzothienyl))](8), [Rh6(CO)14(µ,2-Ph2P(2-thienyl))](9), [Rh6(CO)14(µ,2-PhP(2-thienyl)2)](10) and [Rh6(CO)14(µ,2-Ph2P(pyridyl))](12) clusters have been determined by X-ray crystallography. The various types of chirality exhibited by these clusters are discussed. A simple model is proposed to account for the ratios of stereochemical isomers found in the Rh6(CO)14(µ,2-PhP(2-thienyl)2 cluster. The kinetics of formation of the bridged clusters from the monosubstituted [Rh6(CO)15(1-PX)] clusters have been studied. (Less)
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https://lup.lub.lu.se/record/128391
- author
- Tunik, S P ; Koshevoy, I O ; Poe, A J ; Farrar, D H ; Nordlander, Ebbe LU ; Pakkanen, T A and Haukka, M
- organization
- publishing date
- 2003
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Dalton Transactions
- issue
- 12
- pages
- 2457 - 2467
- publisher
- Royal Society of Chemistry
- external identifiers
-
- wos:000183430100014
- scopus:4744338287
- ISSN
- 1477-9234
- DOI
- 10.1039/b300951c
- language
- English
- LU publication?
- yes
- id
- 7eb0f8c6-96c3-4fb8-ab8a-f48e5bd3f981 (old id 128391)
- date added to LUP
- 2016-04-01 11:48:58
- date last changed
- 2022-01-26 18:41:15
@article{7eb0f8c6-96c3-4fb8-ab8a-f48e5bd3f981,
abstract = {{Some intrinsically chiral [Rh6(CO)14(µ,2-PX)] clusters have been synthesized, beginning with reactions of [Rh6(CO)16–x(NCMe)x](x= 1, 2) with PX, where PX represents the bidentate bridging ligands diphenyl(benzothienyl)phosphine (1), diphenyl(2-thienyl)phosphine (2), di(2-thienyl)phenylphosphine (3), tris(2-thienyl)phosphine (4), diphenyl(2-pyridyl)phosphine (5) and diphenylvinylphosphine (6). The ligand tris(2-furyl)phosphine (7) shows no bridging capability. When x= 1 the initial products are the clusters [Rh6(CO)15(1-PX)] which undergo spontaneous CO loss to form [Rh6(CO)14(µ,2-PX)]. The structures of the [Rh6(CO)15(1-PX)] clusters have been elucidated by IR, NMR spectroscopy and FAB-MS spectrometry, and have been found to involve phosphorus atom coordination to a rhodium atom. In addition, the solid state structures of the [Rh6(CO)14(µ,2-Ph2P(2-benzothienyl))](8), [Rh6(CO)14(µ,2-Ph2P(2-thienyl))](9), [Rh6(CO)14(µ,2-PhP(2-thienyl)2)](10) and [Rh6(CO)14(µ,2-Ph2P(pyridyl))](12) clusters have been determined by X-ray crystallography. The various types of chirality exhibited by these clusters are discussed. A simple model is proposed to account for the ratios of stereochemical isomers found in the Rh6(CO)14(µ,2-PhP(2-thienyl)2 cluster. The kinetics of formation of the bridged clusters from the monosubstituted [Rh6(CO)15(1-PX)] clusters have been studied.}},
author = {{Tunik, S P and Koshevoy, I O and Poe, A J and Farrar, D H and Nordlander, Ebbe and Pakkanen, T A and Haukka, M}},
issn = {{1477-9234}},
language = {{eng}},
number = {{12}},
pages = {{2457--2467}},
publisher = {{Royal Society of Chemistry}},
series = {{Dalton Transactions}},
title = {{Chiral hexarhodium clusters containing heterobidentate phosphine ligands, a structural and reactivity study}},
url = {{http://dx.doi.org/10.1039/b300951c}},
doi = {{10.1039/b300951c}},
year = {{2003}},
}