Advanced

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)]

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 (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)
Please use this url to cite or link to this publication:
author
organization
publishing date
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
id
5abb1a3b-23e2-4198-bdd0-d93f977dd17d (old id 5401296)
date added to LUP
2015-05-19 11:40:20
date last changed
2017-01-01 06:27:14
@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},
  keyword      = {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},
  volume       = {430},
  year         = {2015},
}