0000000000888594
AUTHOR
Ahibur Rahaman
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…
Asymmetric hydrogenation of an α-unsaturated carboxylic acid catalyzed by intact chiral transition metal carbonyl clusters – diastereomeric control of enantioselectivity
Twenty clusters of the general formula [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] (P–P* = chiral diphosphine of the ferrocene-based Walphos or Josiphos families) have been synthesised and characterised. The clusters have been tested as catalysts for asymmetric hydrogenation of tiglic acid [trans-2-methyl-2-butenoic acid]. The observed enantioselectivities and conversion rates strongly support catalysis by intact Ru3 clusters. A catalytic mechanism involving an active Ru3 catalyst generated by CO loss from [(μ-H)2Ru3(μ3-S)(CO)7(μ-P–P*)] has been investigated by DFT calculations. peerReviewed
Bridgehead isomer effects in bis(phosphido)-bridged diiron hexacarbonyl proton reduction electrocatalysts
The influence of the substitution, orientation and structure of the phosphido bridges in [Fe2(CO)6(μ-PR2)2] electrocatalysts of proton reduction has been studied. The isomers e,a-[Fe2(CO)6{μ-P(Ar)H}2] (1a(Ar): Ar = Ph, 2′-methoxy-1,1′-binaphthyl (bn′)), e,e-[Fe2(CO)6{μ-P(Ar)H}2] (1b(Ar): Ar = Ph, bn′) were isolated from reactions of iron pentacarbonyl and the corresponding primary phosphine, syntheses that also afforded the phosphinidene-capped tri-iron clusters, [Fe3(CO)9(μ-CO)(μ3-Pbn′)] (2) and [Fe3(CO)9(μ3-PAr)2] (3(Ar), Ar = Ph, bn′). A ferrocenyl (Fc)-substituted dimer [Fe2(CO)6{μ:μ′-1,2-(P(CH2Fc)CH2)2C6H4}] (4), in which the two phosphido bridges are linked by an o-xylyl group, was al…
Synthesis and characterization of chiral phosphirane derivatives of [(μ-H)4Ru4(CO)12] and their application in the hydrogenation of an α,β-unsaturated carboxylic acid
Abstract Ruthenium clusters containing the chiral binaphthyl-derived mono-phosphiranes [(S)-([1,1′-binaphthalen]-2-yl)phosphirane] (S)-1a, [(R)-(2′-methoxy-1,1′-binaphthyl-2-yl)phosphirane] (R)-1b, and the diphosphirane [2,2′-di(phosphiran-1-yl)-1,1′-binaphthalene] (S)-1c have been synthesized and characterized. The clusters are [(μ-H)4Ru4(CO)11((S)-1a)] (S)-2, [(μ-H)4Ru4(CO)11((R)-1b)] (R)-3, 1,1-[(μ-H)4Ru4(CO)10((S)-1c)] (S)-4, [(μ-H)4Ru4(CO)11((S)-binaphthyl-P(s)(H)Et)] (S,Sp)-5, [(μ-H)4Ru4(CO)11((S)-binaphthyl-P(R)(H)Et)] (S,Rp)-6, [(μ-H)4Ru4(CO)11((R)-binaphthyl-P(s)(H)Et)] (R,Sp)-7, [(μ-H)4Ru4(CO)11((R)-binaphthyl-P(R)(H)Et)] (R,Rp)-8 and the phosphinidene-capped triruthenium cluster …
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 1473786: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Carolina Gimbert-Suriñach, Arne Ficks, Graham E. Ball, Mohan Bhadbhade, Matti Haukka, Lee Higham, Ebbe Nordlander, Stephen B. Colbran|2017|Dalton Trans.|46|3207|doi:10.1039/C6DT01494A
CCDC 1043618: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1962572: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1962571: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1531251: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Maitham H. Majeed, Manuel F. Abelairas-Edesa, Arne Ficks, Radwa M. Ashour, Ahibur Rahaman, William Clegg, Matti Haukka, Lee J. Higham, Ebbe Nordlander|2017|J.Organomet.Chem.|849-850|71|doi:10.1016/j.jorganchem.2017.05.031
CCDC 1962575: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1473787: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Carolina Gimbert-Suriñach, Arne Ficks, Graham E. Ball, Mohan Bhadbhade, Matti Haukka, Lee Higham, Ebbe Nordlander, Stephen B. Colbran|2017|Dalton Trans.|46|3207|doi:10.1039/C6DT01494A
CCDC 1981159: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1473789: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Carolina Gimbert-Suriñach, Arne Ficks, Graham E. Ball, Mohan Bhadbhade, Matti Haukka, Lee Higham, Ebbe Nordlander, Stephen B. Colbran|2017|Dalton Trans.|46|3207|doi:10.1039/C6DT01494A
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 1473788: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Carolina Gimbert-Suriñach, Arne Ficks, Graham E. Ball, Mohan Bhadbhade, Matti Haukka, Lee Higham, Ebbe Nordlander, Stephen B. Colbran|2017|Dalton Trans.|46|3207|doi:10.1039/C6DT01494A
CCDC 1962574: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1043620: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1043617: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
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 1531250: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Maitham H. Majeed, Manuel F. Abelairas-Edesa, Arne Ficks, Radwa M. Ashour, Ahibur Rahaman, William Clegg, Matti Haukka, Lee J. Higham, Ebbe Nordlander|2017|J.Organomet.Chem.|849-850|71|doi:10.1016/j.jorganchem.2017.05.031
CCDC 1962573: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1473790: Experimental Crystal Structure Determination
Related Article: Ahibur Rahaman, Carolina Gimbert-Suriñach, Arne Ficks, Graham E. Ball, Mohan Bhadbhade, Matti Haukka, Lee Higham, Ebbe Nordlander, Stephen B. Colbran|2017|Dalton Trans.|46|3207|doi:10.1039/C6DT01494A
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 1531252: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Maitham H. Majeed, Manuel F. Abelairas-Edesa, Arne Ficks, Radwa M. Ashour, Ahibur Rahaman, William Clegg, Matti Haukka, Lee J. Higham, Ebbe Nordlander|2017|J.Organomet.Chem.|849-850|71|doi:10.1016/j.jorganchem.2017.05.031
CCDC 1043616: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
CCDC 1981173: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
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 1043619: Experimental Crystal Structure Determination
Related Article: Ahmed F. Abdel-Magied, Yusuf Theibich, Amrendra K. Singh, Ahibur Rahaman, Isa Doverbratt, Arun K. Raha, Matti Haukka, Michael G. Richmond, Ebbe Nordlander|2020|Dalton Trans.|49|4244|doi:10.1039/C9DT04799A
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