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, AhiburLund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH (author)

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.

Alam, Fakir Rafiqul (author)
Hossain, KamalLund University,Lunds universitet,Kemisk fysik,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Chemical Physics,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)chem-kmh (author)
Abdel-Magied, Ahmed F. (author)
Ghosh, Shishir (author)
Tocher, Derek A. (author)
Haukka, Matti (author)
Kabir, Shariff E. (author)
Nordlander, Ebbe (author)
Hogarth, Graeme (author)
Kemisk fysikEnheten för fysikalisk och teoretisk kemi (creator_code:org_t)

By the author/editor: Rahaman, Ahibur; Alam, Fakir Rafi ...; Hossain, Kamal; Abdel-Magied, Ah ...; Ghosh, Shishir; Tocher, Derek A.; show more...; Haukka, Matti; Kabir, Shariff E ...; Nordlander, Ebbe; Hogarth, Graeme; show less...

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