Phosphine addition to the sigma,pi-thienyl complex [Fe-2(CO)(6)(mu-Th)(mu-PTh2)] (Th = C4H3S): Carbonyl substitution and migratory carbonyl insertion to give the thienyl-acyl complexes [Fe-2(CO)(4)(diphosphine)(mu-O=C-Th)(mu-PTh2)]
(2015) In Inorganica Chimica Acta 430. p.208-215- Abstract
- The reactivity of the sigma,pi-thienyl complex [Fe-2(CO)(6)(mu-Th)(mu-PTh2)] (1) towards a range of phosphines has been studied. With PR3 (R = Ph, Th) carbonyl substitution affords [Fe-2(CO)(5)(PR3)(mu-Th)(mu-PTh2)] (2ab) as the major product, with smaller amounts of the thienylacyl complexes [Fe-2(CO)(5)(PR3)(mu-O=C-Th)(mu-PTh2)] (3ab) resulting from a migratory carbonyl insertion into the thienyl ligand. With diphosphines, thienylacyl complexes are the major products in all cases. With dppm, [Fe-2(CO)(4)(mu-dppm)(mu-O=C-Th)(mu-PTh2)] (4) results in which the diphosphine bridges the ironiron bond, while with other diphosphines the chelate complexes [Fe-2(CO)(4)(kappa(2)-diphosphine)(mu-O=C-Th)(mu-PTh2)] (59) are isolated, as established... (More)
- The reactivity of the sigma,pi-thienyl complex [Fe-2(CO)(6)(mu-Th)(mu-PTh2)] (1) towards a range of phosphines has been studied. With PR3 (R = Ph, Th) carbonyl substitution affords [Fe-2(CO)(5)(PR3)(mu-Th)(mu-PTh2)] (2ab) as the major product, with smaller amounts of the thienylacyl complexes [Fe-2(CO)(5)(PR3)(mu-O=C-Th)(mu-PTh2)] (3ab) resulting from a migratory carbonyl insertion into the thienyl ligand. With diphosphines, thienylacyl complexes are the major products in all cases. With dppm, [Fe-2(CO)(4)(mu-dppm)(mu-O=C-Th)(mu-PTh2)] (4) results in which the diphosphine bridges the ironiron bond, while with other diphosphines the chelate complexes [Fe-2(CO)(4)(kappa(2)-diphosphine)(mu-O=C-Th)(mu-PTh2)] (59) are isolated, as established through crystallographic studies on [Fe-2(CO)(4)(kappa(2)-dppe)(mu-O=C-Th)(mu-PTh2)] (5) and [Fe-2(CO)(4)(kappa(2)-dppb)(mu-O=C-Th)(mu-PTh2)] (9), both of which show that the diphosphine binds selectively to the oxygen-bound metal centre with phosphorus atoms lying trans to the metalmetal bond and mu-PTh2 bridge. With 1,2-bis(diphenylphosphino)benzene (dppb), [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(C6H4)PPh2}(mu-PTh2)] (10) is isolated in low yields and results from cyclometalation of a phenyl ring and putative elimination of thiophene. In a separate experiment, it has been shown that heating 9 results in the slow formation of 10. (C) 2015 Elsevier B.V. All rights reserved. (Less)
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https://lup.lub.lu.se/record/5401296
- author
- Rahaman, Ahibur LU ; Alam, Fakir Rafiqul ; Hossain, Kamal LU ; Abdel-Magied, Ahmed F. ; Ghosh, Shishir ; Tocher, Derek A. ; Haukka, Matti ; Kabir, Shariff E. ; Nordlander, Ebbe and Hogarth, Graeme
- organization
- publishing date
- 2015
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Phosphine, Diiron, Thienyl, Acyl, Migratory insertion, Chelate
- in
- Inorganica Chimica Acta
- volume
- 430
- pages
- 208 - 215
- publisher
- Elsevier
- external identifiers
-
- wos:000352694600027
- scopus:84925864672
- ISSN
- 0020-1693
- DOI
- 10.1016/j.ica.2015.02.027
- 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
- 5abb1a3b-23e2-4198-bdd0-d93f977dd17d (old id 5401296)
- date added to LUP
- 2016-04-01 14:49:13
- date last changed
- 2022-01-28 02:42:20
@article{5abb1a3b-23e2-4198-bdd0-d93f977dd17d,
abstract = {{The reactivity of the sigma,pi-thienyl complex [Fe-2(CO)(6)(mu-Th)(mu-PTh2)] (1) towards a range of phosphines has been studied. With PR3 (R = Ph, Th) carbonyl substitution affords [Fe-2(CO)(5)(PR3)(mu-Th)(mu-PTh2)] (2ab) as the major product, with smaller amounts of the thienylacyl complexes [Fe-2(CO)(5)(PR3)(mu-O=C-Th)(mu-PTh2)] (3ab) resulting from a migratory carbonyl insertion into the thienyl ligand. With diphosphines, thienylacyl complexes are the major products in all cases. With dppm, [Fe-2(CO)(4)(mu-dppm)(mu-O=C-Th)(mu-PTh2)] (4) results in which the diphosphine bridges the ironiron bond, while with other diphosphines the chelate complexes [Fe-2(CO)(4)(kappa(2)-diphosphine)(mu-O=C-Th)(mu-PTh2)] (59) are isolated, as established through crystallographic studies on [Fe-2(CO)(4)(kappa(2)-dppe)(mu-O=C-Th)(mu-PTh2)] (5) and [Fe-2(CO)(4)(kappa(2)-dppb)(mu-O=C-Th)(mu-PTh2)] (9), both of which show that the diphosphine binds selectively to the oxygen-bound metal centre with phosphorus atoms lying trans to the metalmetal bond and mu-PTh2 bridge. With 1,2-bis(diphenylphosphino)benzene (dppb), [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(C6H4)PPh2}(mu-PTh2)] (10) is isolated in low yields and results from cyclometalation of a phenyl ring and putative elimination of thiophene. In a separate experiment, it has been shown that heating 9 results in the slow formation of 10. (C) 2015 Elsevier B.V. All rights reserved.}},
author = {{Rahaman, Ahibur and Alam, Fakir Rafiqul and Hossain, Kamal and Abdel-Magied, Ahmed F. and Ghosh, Shishir and Tocher, Derek A. and Haukka, Matti and Kabir, Shariff E. and Nordlander, Ebbe and Hogarth, Graeme}},
issn = {{0020-1693}},
keywords = {{Phosphine; Diiron; Thienyl; Acyl; Migratory insertion; Chelate}},
language = {{eng}},
pages = {{208--215}},
publisher = {{Elsevier}},
series = {{Inorganica Chimica Acta}},
title = {{Phosphine addition to the sigma,pi-thienyl complex [Fe-2(CO)(6)(mu-Th)(mu-PTh2)] (Th = C4H3S): Carbonyl substitution and migratory carbonyl insertion to give the thienyl-acyl complexes [Fe-2(CO)(4)(diphosphine)(mu-O=C-Th)(mu-PTh2)]}},
url = {{http://dx.doi.org/10.1016/j.ica.2015.02.027}},
doi = {{10.1016/j.ica.2015.02.027}},
volume = {{430}},
year = {{2015}},
}