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Reactions of the sigma,pi-furyl complex [Fe-2(CO)(6)(mu-Fu)(mu-PFu(2))] (Fu = C4H3O) with phosphines: Carbonyl substitution, migratory carbonyl insertion and cyclometallation-induced furan elimination

Rahaman, Ahibur LU ; Alam, Fakir Rafiqul; Ghosh, Shishir; Tocher, Derek A.; Haukka, Matti; Kabir, Shariff E.; Nordlander, Ebbe LU and Hogarth, Graeme (2014) In Journal of Organometallic Chemistry 751. p.326-335
Abstract
The reactivity of the sigma,pi-furyl complex [Fe-2(CO)(6)(mu-Fu)(mu-PFu(2))] (1) towards PPh3 and a range of bidentate phosphines has been studied and a number of different reaction products have been identified. With PPh3, carbonyl substitution affords [Fe-2(CO)(5)(PPh3)(mu-Fu)(mu-PFu(2))] (2) in which the new phosphine is coordinated to the iron center that is sigma-coordinated by the bridging furyl moiety. With small bite-angle diphosphines - bis(diphenylphosphino) methane (dppm) and 1,8-bis(diphenylphosphino) naphthalene (dppn) - carbonyl substitution and migratory carbonyl insertion result to give the furyl-acyl complexes with bridging, [Fe-2(CO)(4)(mu-dppm)(mu-O]CeFu)(mu-PFu(2))] (3), or chelating,... (More)
The reactivity of the sigma,pi-furyl complex [Fe-2(CO)(6)(mu-Fu)(mu-PFu(2))] (1) towards PPh3 and a range of bidentate phosphines has been studied and a number of different reaction products have been identified. With PPh3, carbonyl substitution affords [Fe-2(CO)(5)(PPh3)(mu-Fu)(mu-PFu(2))] (2) in which the new phosphine is coordinated to the iron center that is sigma-coordinated by the bridging furyl moiety. With small bite-angle diphosphines - bis(diphenylphosphino) methane (dppm) and 1,8-bis(diphenylphosphino) naphthalene (dppn) - carbonyl substitution and migratory carbonyl insertion result to give the furyl-acyl complexes with bridging, [Fe-2(CO)(4)(mu-dppm)(mu-O]CeFu)(mu-PFu(2))] (3), or chelating, [Fe-2(CO)(4)(kappa(2)-dppn)(mu-O]CeFu)(mu-PFu(2))] (4), diphosphines, respectively. With the more flexible diphosphines Ph2P(CH2)(n)PPh2 (n = 2, dppe, n = 3, dppp), the cyclometallated products [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(CH2)(n)PPh2}(mu-PFu(2))] (n = 2, 5; n = 3, 6) are isolated as a result of carbonyl substitution and furan elimination, and a similar complex [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(C6H4)PPh2}(mu-PFu(2))] (7) is generated from the more rigid diphosphine bis(diphenylphosphino) benzene (dppb). With bis(diphenylphosphino)-1,1-binaphthalene (1,1-BINAP) the novel tridentate phosphine complex [Fe-2(CO)(5){mu,kappa(3)-C6H4P(C20H12PPh2)C(6)H(4)PFu}] (8) results from the putative coupling of cyclometallated diphosphine and difurylphosphido ligands, following elimination of two equivalents of furan. The crystal structures of 2, 3, 5 and 8 have been determined and allow a detailed insight into the overall reaction profile. (C) 2013 Elsevier B.V. All rights reserved. (Less)
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Contribution to journal
publication status
published
subject
keywords
Diiron, Furyl, Migratory insertion, Cyclometallation, Carbon-phosphorus, bond formation
in
Journal of Organometallic Chemistry
volume
751
pages
326 - 335
publisher
Elsevier
external identifiers
  • wos:000329864700026
  • scopus:84893719400
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2013.05.026
language
English
LU publication?
yes
id
5fcf95fd-c461-4e5f-8d24-e7c0f028cccf (old id 4318566)
date added to LUP
2014-02-25 10:48:18
date last changed
2017-01-01 05:32:02
@article{5fcf95fd-c461-4e5f-8d24-e7c0f028cccf,
  abstract     = {The reactivity of the sigma,pi-furyl complex [Fe-2(CO)(6)(mu-Fu)(mu-PFu(2))] (1) towards PPh3 and a range of bidentate phosphines has been studied and a number of different reaction products have been identified. With PPh3, carbonyl substitution affords [Fe-2(CO)(5)(PPh3)(mu-Fu)(mu-PFu(2))] (2) in which the new phosphine is coordinated to the iron center that is sigma-coordinated by the bridging furyl moiety. With small bite-angle diphosphines - bis(diphenylphosphino) methane (dppm) and 1,8-bis(diphenylphosphino) naphthalene (dppn) - carbonyl substitution and migratory carbonyl insertion result to give the furyl-acyl complexes with bridging, [Fe-2(CO)(4)(mu-dppm)(mu-O]CeFu)(mu-PFu(2))] (3), or chelating, [Fe-2(CO)(4)(kappa(2)-dppn)(mu-O]CeFu)(mu-PFu(2))] (4), diphosphines, respectively. With the more flexible diphosphines Ph2P(CH2)(n)PPh2 (n = 2, dppe, n = 3, dppp), the cyclometallated products [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(CH2)(n)PPh2}(mu-PFu(2))] (n = 2, 5; n = 3, 6) are isolated as a result of carbonyl substitution and furan elimination, and a similar complex [Fe-2(CO)(5){mu,kappa(2)-C6H4PPh(C6H4)PPh2}(mu-PFu(2))] (7) is generated from the more rigid diphosphine bis(diphenylphosphino) benzene (dppb). With bis(diphenylphosphino)-1,1-binaphthalene (1,1-BINAP) the novel tridentate phosphine complex [Fe-2(CO)(5){mu,kappa(3)-C6H4P(C20H12PPh2)C(6)H(4)PFu}] (8) results from the putative coupling of cyclometallated diphosphine and difurylphosphido ligands, following elimination of two equivalents of furan. The crystal structures of 2, 3, 5 and 8 have been determined and allow a detailed insight into the overall reaction profile. (C) 2013 Elsevier B.V. All rights reserved.},
  author       = {Rahaman, Ahibur and Alam, Fakir Rafiqul and Ghosh, Shishir and Tocher, Derek A. and Haukka, Matti and Kabir, Shariff E. and Nordlander, Ebbe and Hogarth, Graeme},
  issn         = {0022-328X},
  keyword      = {Diiron,Furyl,Migratory insertion,Cyclometallation,Carbon-phosphorus,bond formation},
  language     = {eng},
  pages        = {326--335},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Reactions of the sigma,pi-furyl complex [Fe-2(CO)(6)(mu-Fu)(mu-PFu(2))] (Fu = C4H3O) with phosphines: Carbonyl substitution, migratory carbonyl insertion and cyclometallation-induced furan elimination},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2013.05.026},
  volume       = {751},
  year         = {2014},
}