Phosphine addition to the σ,π-thienyl complex [Fe₂(CO)₆(μ-Th)(μ-PTh₂)] (Th = C₄H₃S): Carbonyl substitution and migratory carbonyl insertion to give the thienyl-acyl complexes [Fe₂(CO)₄(diphosphine)(μ-OC-Th)(μ-PTh₂)]

TY - JOUR

T1 - Phosphine addition to the σ,π-thienyl complex [Fe2(CO)6(μ-Th)(μ-PTh2)] (Th = C4H3S)

T2 - Carbonyl substitution and migratory carbonyl insertion to give the thienyl-acyl complexes [Fe2(CO)4(diphosphine)(μ-OC-Th)(μ-PTh2)]

AU - Rahaman, Ahibur

AU - Alam, Fakir Rafiqul

AU - Hossain, Md Kamal

AU - Abdel-Magied, Ahmed F.

AU - Ghosh, Shishir

AU - Tocher, Derek A.

AU - Haukka, Matti

AU - Kabir, Shariff E.

AU - Nordlander, Ebbe

AU - Hogarth, Graeme

N1 - Funding Information: This research has been partially sponsored by the Ministry of Education, Government of the People’s Republic of Bangladesh . We thank the European Commission for an Erasmus Mundus pre-doctoral fellowship (A.R.), the Commonwealth Scholarship Commission (S.G.) and The Royal Society (G.H. and E.N.) for further funding.

PY - 2015/5/1

Y1 - 2015/5/1

N2 - The reactivity of the σ,π-thienyl complex [Fe2(CO)6(μ-Th)(μ-PTh2)] (1) towards a range of phosphines has been studied. With PR3 (R = Ph, Th) carbonyl substitution affords [Fe2(CO)5(PR3)(μ-Th)(μ-PTh2)] (2a-b) as the major product, with smaller amounts of the thienyl-acyl complexes [Fe2(CO)5(PR3)(μ-OC-Th)(μ-PTh2)] (3a-b) resulting from a migratory carbonyl insertion into the thienyl ligand. With diphosphines, thienyl-acyl complexes are the major products in all cases. With dppm, [Fe2(CO)4(μ-dppm)(μ-OC-Th)(μ-PTh2)] (4) results in which the diphosphine bridges the iron-iron bond, while with other diphosphines the chelate complexes [Fe2(CO)4(κ2-diphosphine)(μ-OC-Th)(μ-PTh2)] (5-9) are isolated, as established through crystallographic studies on [Fe2(CO)4(κ2-dppe)(μ-OC-Th)(μ-PTh2)] (5) and [Fe2(CO)4(κ2-dppb)(μ-OC-Th)(μ-PTh2)] (9), both of which show that the diphosphine binds selectively to the oxygen-bound metal centre with phosphorus atoms lying trans to the metal-metal bond and μ-PTh2 bridge. With 1,2-bis(diphenylphosphino)benzene (dppb), [Fe2(CO)5{μ,κ2-C6H4PPh(C6H4)PPh2}(μ-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.

AB - The reactivity of the σ,π-thienyl complex [Fe2(CO)6(μ-Th)(μ-PTh2)] (1) towards a range of phosphines has been studied. With PR3 (R = Ph, Th) carbonyl substitution affords [Fe2(CO)5(PR3)(μ-Th)(μ-PTh2)] (2a-b) as the major product, with smaller amounts of the thienyl-acyl complexes [Fe2(CO)5(PR3)(μ-OC-Th)(μ-PTh2)] (3a-b) resulting from a migratory carbonyl insertion into the thienyl ligand. With diphosphines, thienyl-acyl complexes are the major products in all cases. With dppm, [Fe2(CO)4(μ-dppm)(μ-OC-Th)(μ-PTh2)] (4) results in which the diphosphine bridges the iron-iron bond, while with other diphosphines the chelate complexes [Fe2(CO)4(κ2-diphosphine)(μ-OC-Th)(μ-PTh2)] (5-9) are isolated, as established through crystallographic studies on [Fe2(CO)4(κ2-dppe)(μ-OC-Th)(μ-PTh2)] (5) and [Fe2(CO)4(κ2-dppb)(μ-OC-Th)(μ-PTh2)] (9), both of which show that the diphosphine binds selectively to the oxygen-bound metal centre with phosphorus atoms lying trans to the metal-metal bond and μ-PTh2 bridge. With 1,2-bis(diphenylphosphino)benzene (dppb), [Fe2(CO)5{μ,κ2-C6H4PPh(C6H4)PPh2}(μ-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.

KW - Acyl

KW - Chelate

KW - Diiron

KW - Migratory insertion

KW - Phosphine

KW - Thienyl

UR - http://www.scopus.com/inward/record.url?scp=84925864672&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2015.02.027

DO - 10.1016/j.ica.2015.02.027

M3 - Article

AN - SCOPUS:84925864672

SN - 0020-1693

VL - 430

SP - 208

EP - 215

JO - INORGANICA CHIMICA ACTA

JF - INORGANICA CHIMICA ACTA

M1 - 16445

ER -