Md. Munkir Hossain

Mixed chalcogen carbonyl compounds: IV.Reactivity of Fe2(CO)6(μ-STe) and Fe3(CO)9(μ3-S) (μ3-Te) towards coordinatively unsaturated species☆

Abstract Using Fe 2 (CO) 6 (μ-STe) and Fe 3 (CO) 9 (μ 3 -S)(μ 3 -Te) for the addition of coordinatively unsaturated species, the following new mixed metal, mixed chalcogen compounds have been obtained: Fe 2 (CO) 6 (μ 3 -S)(μ 3 -Te)M(PPh 3 ) 2 (M = Pt, Pd), Fe 2 Ru(CO) 9 (μ 3 -S)(μ 3 -Te) and Fe 4- x Ru x (CO) 11 (μ 4 -S)(μ 4 -Te) ( x = 0–2). The formation of the triphenylphosphine derivatives, Fe 3 (CO) 9 − x (PPh 3 ) x (μ 3 -S)(μ 3 -Te) ( x = 1,2) and Fe 3 (CO) 9 (PPh 3 )(μ 3 -S)(μ 3 -Te) are also reported.

Mixed chalcogen carbonyl compounds: synthesis and characterisation of (CO)6Fe2(μ3-Se)(μ3-Te)Pt(PPh3)2 Fe3(CO)7(PPh3)2(μ3-Se)(μ3-Te)

Abstract An improved method for isolation of pure Fe3(CO)9(μ3-Se)(μ3-Te) and Fe2(CO)6(μ-SeTe) has been developed. The mixed chalcogenide complex (CO)6Fe2(μ3-Se)(μ3-Te)Pt(PPh3)2 is formed exclusively on treatment of Fe2(CO)6(μ3-Se)(μ3-Te) with Pt(C2H4)(PPh3)2, or along with Fe3(PPh3)2(μ3-Se)(μ3-Te) when Fe3(CO)9(μ3-Se)(μ3-Te) is treated with Pt(PPh3)4. With PPh3, Fe3(CO)9(μ3-Se)(μ3-Te) forms an adduct, (CO)6Fe2(μ3-Se)(μ3-Te)Fe(CO)3(PPh3).

TRINUCLEAR AND TETRANUCLEAR IRON RUTHENIUM CARBONYL CLUSTERS STABILIZED BY BRIDGING SELENIUM LIGANDS

Abstract At room temperature, Fe 2 (CO) 6 (μ-Se 2 ) reacts with Ru 3 (CO) 12 to form Fe 2 Ru 3 (CO) 17 (μ 4 -Se)(μ 3 -Se), and with Ru(CO) 4 (C 2 H 2 ) to form Fe 2 Ru(CO) 9 (μ 3 -Se) 2 . The latter reacts with Fe(CO) 5 under visible light irradiation to give Fe 3 Ru(CO) 11 (μ 4 -Se) 2 , and with Ru(CO) 4 (C 2 H 4 ) to form Fe 2 Ru 2 (CO) 11 (μ 4 -Se) 2 . Visible light irradiation of a solution containing Fe 3 (CO) 9 (μ 3 -Se) 2 and Fe(CO) 5 yields Fe 4 (CO) 11 (μ 4 -Se) 2 . A solution containing Fe 3 (CO) 9 (μ 3 -Se) 2 and Ru(CO) 4 (C 2 H 4 ) at room temperature with stirring yielded Fe 3 Ru(CO) 11 (μ 4 -Se) 2 .

Mixed chalcogen carbonyl compounds: III. Construction of the new unsaturated mixed metal clusters Fe2Ru2(CO)10(μ-CO)(μ4-Se)(μ4-Te) and Fe3Ru(CO)10(μ-CO)(μ4-Te)☆

Abstract Addition of Ru(CO) 4 (C 2 H 4 )to Fe 2 Ru(CO) 9 (μ 3 -Se)(μ 3 -Te) and Fe 3 (CO) 9 (μ 3 -Se)(μ 3 -Te) lead to a clean formation of the new unsaturated mixed metal, mixed chalcogen carbonyl clusters, Fe 2 Ru 2 (CO) 10 (μ-CO)(μ 4 -Se)(μ 4 -Te) and Fe 3 Ru(CO) 10 (μ-CO)(μ 4 -Se)(μ 4 -Te) respectively. The Fe 3 Ru cluster is also obtainable from the photolysis of a solution containing Fe 2 Ru(CO) 9 (μ 3 -Se)(μ 3 -Te) and Fe(CO) 5 .

Mixed chalcogen carbonyl compounds: II. Synthesis and characterization of Fe2Ru(μ3-Se)(μ3-Te)(CO)9 and (μ5-C5H5)CoFe2(μ3-Se)(μ3-Te)(CO)6

The new mixed metal complexes, each containing bridging selenium and tellurium ligands in the same molecule, Fe 2 Ru(CO) 9 (μ 3 -Se)(μ 3 -Te) and (η 5 -C 5 H 5 )CoFe 2 (CO) 6 (μ 3 -Se)(μ 3 -Te) have been prepared from the room temperature reactions of Fe 2 (CO) 6 (μ-SeTe) with Ru(CO) 4 (C 2 H 4 ) and (C 5 H 5 )Co(CO) 2 , respectively. Reaction of (η 5 -C 5 H 5 )CoFe 2 (CO) 6 (μ 3 -Se)(μ 3 -Te) with Pt(PPh 3 ) 4 forms the previously known (CO) 6 Fe 2 (μ 3 -Se)(μ 3 -Te)Pt(PPh 3 ) 2 and on treatment with NaOMe, followed by acidification, Fe 2 (CO) 6 (μ-SeTe) is formed.

Facile synthesis of Ru4(CO)10(μ-CO)(μ4-Se)2 and its reactions with phosphine ligands

Abstract The title compound has been prepared by refluxing a benzene solution containing Fe3(CO)9(μ3-Se)2 and Ru3(CO)12 or by stirring a benzene solution containing Ru3(CO)9(/gm3-Se)2 and Ru(CO)4(C2H4) at room temperature. Its reactions with triphenylphosphine, bis(diphenylphosphino)methane and bis(diphenylphosphino)ethane give tetraruthenium and triruthenium phosphine derivatives.

Molecular structures of Fe4(CO)10(μ-CO)(μ4-Se) 2 and Fe3Ru(CO)10(μ-CO)(μ4-Se)2

The results of the X-ray analyses of Fe 4 (CO) 10 (μ-CO)(μ 4 -Se) 2 and Fe 3 Ru(CO) 10 (μ-CO)(μ 4 -Se) 2 are reported. The two compounds are isomorphous and belong to the orthorhombic space group Pccn with a = 6.655(1), b = 15.587(2), c = 17.387(2) A for Fe 4 (CO) 10 (μ-CO)(μ 4 -Se) 2 and a = 6.630(1), b = 15.785(2), c = 17.629(3) A for Fe 3 Ru(CO) 10 (μ-CO)(μ 4 -Se) 2 . The structures were solved by direct methods and refined, correcting for extinction, to R = 0.0306 and 0.0312 for 1171 and 1277 observed reflections for Fe 4 (CO) 10 (μ-CO)(μ 4 -Se) 2 and Fe 3 Ru(CO) 10 (μ-CO)(μ 4 -Se) 2 respectively. They belong to the [M 4 (CO) 11 XY] clusters which are formally unsaturated according to the 18-electron rules but conform to the Wades rules of electron counting. Both complexes contain terminal, bridging and semibridging carbonyl groups.

Synthesis and characterisation of the methylene-inserted mixed-chalcogenide compounds Fe2(CO)6(μ-SeCH2Te) and Fe2(CO)6(μ-SCH2Te)

The methylene-bridged, mixed-chalogen compounds Fe2(CO)6(μ-SeCH2Te) (1) and Fe2(CO)6(μ-SCH2Te) (3) have been synthesised from the room temperature reaction of diazomethane with Fe2(CO)6(μ-SeTe) and Fe2(CO)6(μ-STe), respectively. Compounds 1 and 3 have been characterised by IR, 1H, 13C, 77Se and 125Te NMR spectroscopy. The structure of 1 has been elucidated by X-ray crystallography. The crystalsare monoclinic,space group P21/n, a = 6.695(2), b = 13.993(5), c = 14.007(4)A, β = 103.03(2)°, V = 1278(7) A3, Z = 4, Dc = 2.599 g cm−3 and R = 0.030 (Rw = 0.047).

Thermolysis of Fe3(CO)9(μ3-Se)(μ3-E) (E = S, Te) with Cp2Mo2(CO)6 and formation of new mixed-chalcogenide, mixed Fe-Mo carbonyl clusters. Crystal structures of Cp2Mo2Fe2(CO)6(μ3-Se)2(μ4-Te), Cp2Mo2Fe2(CO)7(μ3-Se)(μ3-Te) and Cp2Mo2Fe2(CO)6(μ3-S)(μ3-Se)(μ4-Se)

Abstract The thermolytic reaction of Fe3(CO)9(μ3-Se)(μ3-Te) with Cp2Mo2(CO)6 in benzene yielded the new mixed-metal, mixed trichalcogenide clusters Cp2Mo2Fe2(CO)6(μ3-Se)(μ3-Te)(μ4-Te) (2a), Cp2Mo2Fe2(CO)6(μ3-Te)2(μ4-Se) (2b) and Cp2Mo2Fe2(CO)6(μ3-Se)2(μ4-Te) (3a), Cp2Mo2Fe2(CO)6(μ3-Se)(μ3-Te)(μ4-Se) (3b) as well as the dichalcogenide cluster Cp2Mo2Fe2(CO)7(μ3-Se)(μ3-Te) (8). Similarly, the thermolysis of Fe3(CO)9(μ3-S)(μ3-Se) with Cp2Mo2(CO)6 in benzene afforded the new mixed-metal, mixed trichalcogenide clusters Cp2Mo2Fe2(CO)6(μ3-S)2(μ4-Se) (10), Cp2Mo2Fe2(CO)6(μ3-S)(μ3-Se)(μ4-Se) (11) and the dichalcogenide cluster Cp2Mo2Fe2(CO)7(μ3-S)(μ3-Se) (13). In the case of 10 and 11, formation of isomers containing the sulphido in the μ4-site was not observed. Compounds 2a and 2b could also be obtained when Cp2Mo2Fe2(CO)6(μ3-Te)2 was refluxed with selenium powder in benzene. Similarly, refluxing of benzene solutions containing selenium powder and Cp2Mo2Fe2(CO)6(μ3-Se)(μ3-Te) formed 3a and 3b, and sulphur powder with Cp2Mo2Fe2(CO)6(μ3-S)(μ3-Se) or Cp2Mo2Fe2(CO)6(μ3-Se)2 yielded the compounds 10 and 11 respectively. The new clusters have been characterised by IR and by 1H, 13C, 77Se and 125Te NMR spectroscopy. Clusters 3a, 8 and 11 have also been structurally characterised by single-crystal X-ray diffraction methods.

Diyne-bridged metal clusters: Synthesis and spectroscopic characterization of [(CO)6Fe2Se2{μ-HCC(CCR)}M](R Me and nBu; M Cp2 Mo2(CO)4, Co2(CO)6, Ru3(CO)10 and Os3(CO)10). Structural characterization of [(CO) 6Fe2Se2{μ-HCC(CCnBu)}Cp2Mo2(CO)4] and [(CO)6Fe2Se2{μ-HCC(CCMe)}Ru3(CO)10]

Abstract Room temperature reaction of [(CO)6Fe2{μ-SeC(H)C(CCR)Se}], with the dimetallic species, Cp2Mo2(CO)4 and Co2(CO)8, afforded the adducts [(CO)6Fe2Se2(μ-HCC(CCR))Cp2Mo2(CO)4] (R  Me, 1; R  nBu, 2) and [(CO)6Fe2Se2(μ-HCC(CCR))Co2(CO)6] (R  Me, 3; R  nBu, 4) respectively. On reaction of Ru3(CO)10 (NCMe)2 with [(CO)6Fe2(μ-SeC(H)C(CCR)Se)], the new diyne-bridged mixed-metal clusters [(CO)6Fe2Se2(μ-HCC(CCR))Ru3(CO)10] (R  Me, 5; R  nBu, 6) were obtained. Similarly, [(CO)6Fe2Se2(μ-HCC(CCnBu))Os3(CO)10], 7, was isolated from the reaction of [(CO)6Fe2(μ-SeC(H)C(CCnBu)Se)] with Os3(CO)10(NCMe)2. Compounds 1–7 were characterized by IR and 1H, 13C and 77Se NMR spectroscopy. The structures of 2 and 5 were established by single crystal X-ray diffraction study. Both contain an Fe2Se2 butterfly core bridged by an HCC unit of the diyne HCCCCR across the two Se atoms. In 2, the substituted acetylenic moiety is transversely bridged to the MoMo bond and in 5, it forms a μ3-//η2 bridge to an Ru3 triangular core.