Manganese

waheedjj's picture

The Catalytic Activity of Poly(Siloxane)- Supported ‎Metalloporphyrins in Olefin Oxidation Reactions: The ‎Effect of the Support on the Catalytic Activity and ‎Selectivity

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical Volume 113, Issues 1–2, Pages 35–44
Year of Publication: 
1996
Authors: 
Waheed Jondi
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Hikmat S. Hilal
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Shukri Khalaf
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Afaq Keilani
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Mohammad Suleiman
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Mohammad Suleiman
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
A.F. Schreiner
Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204, USA
Preferred Abstract (Original): 

Supported tetra(-4-pyridyl)porphyrinato-manganese(III) [MnIII(TPyP)]+ and -tin(IV) [SnIV(TPyP)]2+ have been prepared. The solid support was iodonated poly(siloxane) surface prepared by condensation reactions of (EtO)4Si with (MeO)3Si(CH2)3I. The supported metalloporphyrins were employed as catalysts for the oxidation reactions of 1-octene and of cyclohexene. NaBH4 was used to reduce [MnIII(TPyP)]+ and [SnIV(TPyP)]2+ back to their catalytically active MnII and SnII forms, respectively. Contrary to their homogeneous counterparts, both of the supported metalloporphyrins catalysed the cyclohexene oxidation reaction to yield only 2-cyclohexen-1-one with no other products over a reaction time of 10 h. In addition to cyclohexene oxidation, the supported [MnIII(TPyP)]+ catalysed 1-octene oxidation as well, whereas the supported [SnIV(TPyP)]2+ was inactive for the oxidation of 1-octene.

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shkhalaf's picture

The Catalytic Activity of Poly(Siloxane)-Supported Metalloporphyrins in Olefin Oxidation ‎Reactions: The Effect of The Support on the Catalytic Activity and Selectivity

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical, Volume 113, Number 1, pp. 35-44(10)
Year of Publication: 
1996
Authors: 
Khalaf, S.
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Jondi, W.
Hilal, H.S.
Keilani, A.
Suleiman, M.
Schreiner, A.F.
Preferred Abstract (Original): 
Supported tetra(-4-pyridyl)porphyrinato-manganese(III)[MnIII(TPyP)]+ and -tin(IV)[SnIV(TPyP)]2+ have been prepared. The solid support was iodonated poly(siloxane) surface prepared by condensation reactions of (EtO)4Si with (MeO)3Si(CH2)3I. The supported metalloporphyrins were employed as catalysts for the oxidation reactions of l-octene and of cyclohexene. NaBH4 was used to reduce [MnIII(TPyP)]+ and [SnIV(TPyP)]2+ back to their catalytically active MnII and SnII forms, respectively. Contrary to their homogeneous counterparts, both of the supported metalloporphyrins catalysed the cyclohexene oxidation reaction to yield only 2-cyclohexen-1-one with no other products over a reaction time of 10 h. In addition to cyclohexene oxidation, the supported [MnIII(TPyP)]+ catalysed l-octene oxidation as well, whereas the supported [SnIV(TPyP)]2+ was inactive for the oxidation of l-octene.

see the full file here
Hikmat S. Hilal's picture

Investigation of the Catalytic Activity of Poly (Siloxane)-Supported Tetra (4-Pyridyl) Porphyrinatomanganese (III) in Olefin Oxidation Reactions

Journal Title, Volume, Page: 
Journal of Molecular Catalysis Volume 81, Issue 2, 10 May 1993, Pages 157-165
Year of Publication: 
1993
Authors: 
Hikmat S. Hilal
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Current Affiliation: 
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
C. Kim
Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204 USA
A. F. Schreiner
Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204 USA
Preferred Abstract (Original): 

Supported tetra(4-pyridyl)porphyrinatomanganese(III), [MnIII (TPyP)]+, has been used as a chemically regenerated catalyst for the oxidation of cyclohexene to cyclohex-2-en-1-one. NaBH4 was used to reduce [MnIII(TPyP)]+ back to its catalytically active MnIII form. The reaction was selective to produce the cyclohexenone, and the catalyst showed high activity, with turnovers up to 14 × 103. The effects of solvent, temperature, recovery, and reactant concentrations on the rate of the reaction have also been studied. The rate of the reaction was first order with respect to the catalyst. At higher olefin or oxygen concentrations the reaction was slower. A slower reaction was observed also in the absence of NaBH4. The reaction was faster in nonpolar solvents than in polar ones. These results are also discussed.

Hikmat S. Hilal's picture

The catalytic activity of poly(siloxane)-supported metalloporphyrins in olefin oxidation reactions: the effect of the support on the catalytic activity and selectivity

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical Volume 113, Issues 1-2, 25 November 1996, Pages 35-44
Year of Publication: 
1996
Authors: 
Hikmat S. Hilal
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Current Affiliation: 
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Waheed Jondi
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Shukri Khalaf
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Afaq Keilani
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Mohammad Suleiman
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
A. F. Schreiner
Department of Chemistry, North Carolina State University, Raleigh, NC 27695-8204, USA
Preferred Abstract (Original): 

Supported tetra(-4-pyridyl)porphyrinato-manganese(III) [MnIII(TPyP)]+ and -tin(IV) [SnIV(TPyP)]2+ have been prepared. The solid support was iodonated poly(siloxane) surface prepared by condensation reactions of (EtO)4Si with (MeO)3Si(CH2)3I. The supported metalloporphyrins were employed as catalysts for the oxidation reactions of 1-octene and of cyclohexene. NaBH4 was used to reduce [MnIII(TPyP)]+ and [SnIV(TPyP)]2+ back to their catalytically active MnII and SnII forms, respectively. Contrary to their homogeneous counterparts, both of the supported metalloporphyrins catalysed the cyclohexene oxidation reaction to yield only 2-cyclohexen-1-one with no other products over a reaction time of 10 h. In addition to cyclohexene oxidation, the supported [MnIII(TPyP)]+ catalysed 1-octene oxidation as well, whereas the supported [SnIV(TPyP)]2+ was inactive for the oxidation of 1-octene.

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