0000000000410365
AUTHOR
George C. Lisensky
Chalcogenide-capped triiron clusters [Fe3(CO)9(μ3-E)2], [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) as proton-reduction catalysts
Chalcogenide-capped triiron clusters [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] and [Fe3(CO)7(μ3-E)2(μ-dppm)] (E = S, Se) have been examined as proton-reduction catalysts. Protonation studies show that [Fe3(CO)9(μ3-E)2] are unaffected by strong acids. Mono-capped [Fe3(CO)7(μ3-CO)(μ3-E)(μ-dppm)] react with HBF4.Et2O but changes in IR spectra are attributed to BF3 binding to the face-capping carbonyl, while bicapped [Fe3(CO)7(μ3-E)2(μ-dppm)] are protonated but in a process that is not catalytically important. DFT calculations are presented to support these protonation studies. Cyclic voltammetry shows that [Fe3(CO)9(μ3-Se)2] exhibits two reduction waves, and upon addition of strong acids, proton-reducti…
Proton reduction by phosphinidene-capped triiron clusters
Bis(phosphinidene)-capped triiron carbonyl clusters, including electron rich derivatives formed by substitution with chelating diphosphines, have been prepared and examined as proton reduction catalysts. Treatment of the known cluster [Fe3(CO)9(µ3-PPh)2] (1) with various diphosphines in refluxing THF (for 5, refluxing toluene) afforded the new clusters [Fe3(CO)7(µ3-PPh)2(κ2-dppb)] (2), [Fe3(CO)7(µ3-PPh)2(κ2-dppv)] (3), [Fe3(CO)7(µ3-PPh)2(κ2-dppe)] (4) and [Fe3(CO)7(µ3-PPh)2(µ-κ2-dppf)] (5) in moderate yields, together with small amounts of the corresponding [Fe3(CO)8(µ3-PPh)2(κ1-Ph2PxPPh2)] cluster (x = -C4H6-, -C2H2-, -C2H4-, -C3H6-, -C5H4FeC5H4-). The molecular structures of complexes 3 a…
Oxovanadium(V) complexes with tripodal bisphenolate and monophenolate ligands: Syntheses, structures and catalytic activities
Abstract The reactions between [VO(acac)2] (acac– = acetylacetonate) and the tripodal amino bisphenols 6,6′-(((2-morpholinoethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L1) and 6,6′-(((thiophen-2-ylmethyl)azanediyl)bis(methylene))bis(2,4-di-tert-butylphenol) (H2L2) as well as the tetradentate amino phenol 2,2′-((3,5-di-tert-butyl-2-hydroxybenzyl)azanediyl)bis(ethan-1-ol) (H3L3) afford the complexes [VO(L1)(OMe)] (1), [VO(L2)(acac)] (2) and [VO(L3)] (3), correspondingly. Complexes 1 and 3 can also be prepared using VOSO4·xH2O or [VO(OPr)3] as vanadium precursors. When [VO(acac)2] or VOSO4·xH2O is used, mononuclear oxovanadium(V) complexes are formed upon oxidation of the met…
An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand
[W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal oxidation s…
Nonheme Fe(IV) Oxo Complexes of Two New Pentadentate Ligands and Their Hydrogen-Atom and Oxygen-Atom Transfer Reactions.
Two new pentadentate {N5} donor ligands based on the N4Py (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) framework have been synthesized, viz. [N-(1-methyl-2-benzimidazolyl)methyl-N-(2-pyridyl)methyl-N-(bis-2-pyridyl methyl)amine] (L1) and [N-bis(1-methyl-2-benzimidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L2), where one or two pyridyl arms of N4Py have been replaced by corresponding (N-methyl)benzimidazolyl-containing arms. The complexes [FeII(CH3CN)(L)]2+ (L = L1 (1); L2 (2)) were synthesized, and reaction of these ferrous complexes with iodosylbenzene led to the formation of the ferryl complexes [FeIV(O)(L)]2+ (L = L1 (3); L2 (4)), which were characterized by UV–vis spe…
An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand
Abstract [W(N2O2)(HN2O2)] (H4N2O2 = N,N′-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)3] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal ox…
Synthesis of phosphine derivatives of [Fe2(CO)6(μ-sdt)] (sdt = SCH2SCH2S) and investigation of their proton reduction capabilities
The reactions of [Fe2(CO)6(μ-sdt)] (1) (sdt = SCH2SCH2S) with phosphine ligands have been investigated. Treatment of 1 with dppm (bis(diphenylphosphino)methane) or dcpm (bis(dicyclohexylphosphino)methane) affords the diphosphine-bridged products [Fe2(CO)4(μ-sdt)(μ-dppm)] (2) and [Fe2(CO)4(μ-sdt)(μ-dcpm)] (3), respectively. The complex [Fe2(CO)4(μ-sdt)(κ2-dppv)] (4) with a chelating diphosphine was obtained by reacting 1 with dppv (cis-1,2-bis(diphenylphosphino)ethene). Reaction of 1 with dppe (1,2-bis(diphenylphosphino)ethane) produces [{Fe2(CO)4(μ-sdt)}2(μ-κ1-dppe)] (5) in which the diphosphine forms an intermolecular bridge between two diiron cluster fragments. Three products were obtaine…
CCDC 1418388: Experimental Crystal Structure Determination
Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564
CCDC 1033835: Experimental Crystal Structure Determination
Related Article: Mainak Mitra , Hassan Nimir , Serhiy Demeshko , Satish S. Bhat , Sergey O. Malinkin , Matti Haukka , Julio Lloret-Fillol , George C. Lisensky , Franc Meyer , Albert A. Shteinman , Wesley R. Browne , David A. Hrovat , Michael G.Richmond , Miquel Costas , Ebbe Nordlander|2015|Inorg.Chem.|54|7152|doi:10.1021/ic5029564
CCDC 1518695: Experimental Crystal Structure Determination
Related Article: Md. Kamal Hossain, Matti Haukka, George C. Lisensky, Ari Lehtonen, Ebbe Nordlander|2019|Inorg.Chim.Acta|487|112|doi:10.1016/j.ica.2018.11.049
CCDC 1518696: Experimental Crystal Structure Determination
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CCDC 1896756: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, George C. Lisensky, Matti Haukka, Derek A. Tocher, Michael G. Richmond, Stephen B. Colbran, Ebbe Nordlander|2021|J.Organomet.Chem.|943|121816|doi:10.1016/j.jorganchem.2021.121816
CCDC 1473054: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Shishir Ghosh, Sucharita Basak-Modi, Ahmed F. Abdel-Magied, Shariff E. Kabir, Matti Haukka, Michael G. Richmond, George C. Lisensky, Ebbe Nordlander, Graeme Hogarth|2019|J.Organomet.Chem.|880|213|doi:10.1016/j.jorganchem.2018.10.018
CCDC 1473051: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Shishir Ghosh, Sucharita Basak-Modi, Ahmed F. Abdel-Magied, Shariff E. Kabir, Matti Haukka, Michael G. Richmond, George C. Lisensky, Ebbe Nordlander, Graeme Hogarth|2019|J.Organomet.Chem.|880|213|doi:10.1016/j.jorganchem.2018.10.018
CCDC 1896754: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, George C. Lisensky, Matti Haukka, Derek A. Tocher, Michael G. Richmond, Stephen B. Colbran, Ebbe Nordlander|2021|J.Organomet.Chem.|943|121816|doi:10.1016/j.jorganchem.2021.121816
CCDC 1822503: Experimental Crystal Structure Determination
Related Article: Md. Kamal Hossain, Matti Haukka, Mikko M. Hänninen, George C. Lisensky, Petriina Paturi, Ebbe Nordlander, Ari Lehtonen|2018|Inorg.Chem.Commun.|93|149|doi:10.1016/j.inoche.2018.05.023
CCDC 1896755: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, George C. Lisensky, Matti Haukka, Derek A. Tocher, Michael G. Richmond, Stephen B. Colbran, Ebbe Nordlander|2021|J.Organomet.Chem.|943|121816|doi:10.1016/j.jorganchem.2021.121816
CCDC 1518697: Experimental Crystal Structure Determination
Related Article: Md. Kamal Hossain, Matti Haukka, George C. Lisensky, Ari Lehtonen, Ebbe Nordlander|2019|Inorg.Chim.Acta|487|112|doi:10.1016/j.ica.2018.11.049
CCDC 994961: Experimental Crystal Structure Determination
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