Isomerization

waheedjj's picture

Poly (Siloxane)-Supported ‎Decacarbonyldimanganese(0) Catalyst for Terminal ‎Olefin Hydrosilylation Reactions: The Effect of the ‎Support on the Catalyst Selectivity, Activity and ‎Stability

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical Volume 144, Issue 1, Pages 47–59
Year of Publication: 
1999
Authors: 
Waheed J. 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
Moayyad M. Masoud
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Mohammad A. Suleiman
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
Preferred Abstract (Original): 

A new class of supported carbonyl manganese catalyst was prepared by treating the dimeric decacarbonyldimanganese(0), Mn2(CO)10, with insoluble aminated poly(siloxane) surface. Solid state FT-IR spectra indicated that the supported catalyst is a dimeric complex that is substituted with two amine ligands, one at each Mn atom. The supported manganese complex was investigated as catalyst for the hydrosilylation reaction of terminal olefins. Contrary to the homogeneous Mn2(CO)10 catalytic system, the supported manganese complex was completely selective toward the hydrosilylation reaction with no detectable olefin isomerization or other side-reaction products. Furthermore, the catalyst was selective to produce the linear hydrosilylation product rather than the branched one. No lowering in catalyst activity due to the support was observed. A good proportion of the catalyst activity after separation and reuse was retained for at least four times. Highly reproducible catalytic activity measurements were obtained with catalytic samples taken from same prepared batch. Different prepared batches showed lower reproducibility. The effect of different reaction parameters, such as the solvent effect, the temperature effect, the concentration effect and the added-ligand effect have also been studied. Laine's kinetic studies indicated that the cluster remained intact during the reaction.

shkhalaf's picture

Terminal Olefin Isomerization Reactions Catalyzed by Poly(Siloxane)-Supported Ru3(CO)12: The Effect of The Support on the Catalyst Selectivity, Activity and Stability

Journal Title, Volume, Page: 
Al-Azhar University Journal, Gaza, Vol. 1, No. 1, 1-21
Year of Publication: 
1999
Authors: 
Shukri Khalaf
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
Mohammad A. Sulaiman
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Waheed J. Jondi
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Moayyad Massoud
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Preferred Abstract (Original): 

Dodecacarbonyltriruthenium(0), Ru3(CO)12, 1, has been chemically anchored to the aminated polysiloxane surface, 2. The resulting supported ruthenium complex, 3, was evaluated as catalyst for the olefin isomerization reactions. Contrary to its homogeneous catalyst counterpart, 1, the supported catalyst 3 showed exceptionally high selectivity towards 1-octene isomerizationand trans-2-octene was the sole product of the reaction mixture. The olefin isomerization reaction was markedly activated by the presence of the tertiary silane (EtO)3SiH. No hydrosilylation reaction products were detected. Preliminary kinetic study indicated catalysis by lower nuclearity catalytic species, where the cluster fragments during the reaction process. The effects of different reaction parameters on the rate of the reaction have been investigated.
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shkhalaf's picture

Poly (Siloxane)-Supported ‎Decacarbonyldimanganese(0) Catalyst for Terminal ‎Olefin Hydrosilylation Reactions: The Effect of the ‎Support on the Catalyst Selectivity, Activity and ‎Stability

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical Volume 144, Issue 1, Pages 47–59
Year of Publication: 
1999
Authors: 
Shukri Khalaf
Department of Chemistry, An-Najah N. University, P.O. Box 7, Nablus, Palestine
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
Hikmat S. Hilal
Department of Chemistry, An-Najah N. University, P.O. Box 7, Nablus, Palestine
Mohammad A. Suleiman
Department of Chemistry, An-Najah N. University, P.O. Box 7, Nablus, Palestine
Waheed J. Jondi
Department of Chemistry, An-Najah N. University, P.O. Box 7, Nablus, Palestine
Moayyad M. Masoud
Department of Chemistry, An-Najah N. University, P.O. Box 7, Nablus, Palestine
Preferred Abstract (Original): 

A new class of supported carbonyl manganese catalyst was prepared by treating the dimeric decacarbonyldimanganese(0), Mn2(CO)10, with insoluble aminated poly(siloxane) surface. Solid state FT-IR spectra indicated that the supported catalyst is a dimeric complex that is substituted with two amine ligands, one at each Mn atom. The supported manganese complex was investigated as catalyst for the hydrosilylation reaction of terminal olefins. Contrary to the homogeneous Mn2(CO)10 catalytic system, the supported manganese complex was completely selective toward the hydrosilylation reaction with no detectable olefin isomerization or other side-reaction products. Furthermore, the catalyst was selective to produce the linear hydrosilylation product rather than the branched one. No lowering in catalyst activity due to the support was observed. A good proportion of the catalyst activity after separation and reuse was retained for at least four times. Highly reproducible catalytic activity measurements were obtained with catalytic samples taken from same prepared batch. Different prepared batches showed lower reproducibility. The effect of different reaction parameters, such as the solvent effect, the temperature effect, the concentration effect and the added-ligand effect have also been studied. Laine's kinetic studies indicated that the cluster remained intact during the reaction.

see the full file here

warad's picture

1H 13C NMR Investigation of E/Z-Isomerization around C N Bond In the Trans-Alkene-Pt(II)Imine Complexes of Some Ketimines and Aldimines

Journal Title, Volume, Page: 
Journal of Saudi Chemical Society
Year of Publication: 
2010
Authors: 
M. Bakkar
Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
M. Monshi
Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
I. Warad
Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
Current Affiliation: 
Department of Chemistry, Faculty of Science, An-Najah National University, Nablus, Palestine
M. Siddiqui
Department of Chemistry, College of Science, Taibah University, Madinah, Saudi Arabia
A. Bahajaj
Department of Chemistry, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
Preferred Abstract (Original): 
Ketimines (K1, K2) and aldimines (A1, A2, and A3) were prepared from unsubstituted acetophenone and/or benzaldehyde and primary amines (i-PrNH2, i-BuNH2 and t-BuNH2). These imines were reacted with Zeise’s salt (potassium ethenetrichloroplatinate(II)) to produce the respective complexes, namely, PtK1, PtK2, PtA1, PtA2, and PtA3. 1H, 13C, and 195Pt-chemical shifts of the ligands and their complexes were studied to investigate the nature and mode of isomerization around C N bond. The aldimines and their complexes were obtained as a single isomer. On the other hand, the ketimines and their complexes were obtained as a mixture of E/Z-isomers. It was found that the aldimine- and ketimine-platinum complexes undergo slow E/Z-isomerization in solution as evidenced from NMR spectra.
Hikmat S. Hilal's picture

Terminal Olefin Isomerization Reactions Catalyzed by Poly(Siloxane)-Supported Ru3(CO)12 : The Effect of The Support on the Catalyst Selectivity, Activity and Stability

Journal Title, Volume, Page: 
Al-Azhar University Journal, Gaza, Vol. 1, No. 1,( 1999), 1-21
Year of Publication: 
1999
Authors: 
Hikmat S. Hilal
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Current Affiliation: 
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Mohammad A. Sulaiman
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Waheed J. Jondi
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Shukri Khalaf
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Moayyad Massoud
Department of Chemistry, An-Najah N. University, Nablus, P.O Box 7, West Bank, Palestine
Preferred Abstract (Original): 

Dodecacarbonyltriruthenium(0), Ru3(CO)12, 1, has been chemically anchored to the aminated polysiloxane surface, 2. The resulting supported ruthenium complex, 3, was evaluated as catalyst for the olefin isomerization reactions. Contrary to its homogeneous catalyst counterpart, 1, the supported catalyst 3 showed exceptionally high selectivity towards 1-octene isomerization, and trans-2-octene was the sole product of the reaction mixture. The olefin isomerization reaction was markedly activated by the presence of the tertiary silane (EtO)3SiH. No hydrosilylation reaction products were detected. Preliminary kinetic study indicated catalysis by lower nuclearity catalytic species, where the cluster fragments during the reaction process. The effects of different reaction parameters on the rate of the reaction have been investigated.

Hikmat S. Hilal's picture

Short Communication: The Mechanism of 1- Octene Isomerization and Hydrosilylation Reaction Catalysed by Ru3(CO)12

Journal Title, Volume, Page: 
An-Najah J. Res., Vol. II, No. 8, P:175-183
Year of Publication: 
1994
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
Preferred Abstract (Original): 

Isomerization and hydrosilylation reactions of terminal olefins have been reported under thermal and photochemical conditions using Ru3 (C0) 12, 1, and HRu3 (CO)!!, 2,11 '0 In a very recent work, we reported E LI that 1 catalyses both Isomerization and hydrosilylation reactions of 1-octene (eq. 1). It has been found that the isomerization reaction occurs via lower nuclearity catalytic species that result from fragmentation of the mother cluster 1. Evidence in favour of concurrent cluster catalysis was also reported. On the other hand, the hydrosilylation reaction occurred via cluster catalysis at first and after some-time fragment catalysis occurred.

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Hikmat S. Hilal's picture

Olefin Hydrogenation and Isomerization Catalysed by Ru3(CO)12 and its Derivatives. Cluster vs. Non-Cluster Catalysis

Journal Title, Volume, Page: 
Journal Of Organometallic Chemistry Volume 452, Issues 1-2, 15 June 1993, Pages 161-165
Year of Publication: 
1993
Authors: 
H. 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
W. Jondi
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
S. Khalaf
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
R. Abu-Halawa
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Preferred Abstract (Original): 

The systems Ru3(CO)12·nL, (L = PPh3, CH3CN, (EtO)3Si(CH2)3NH2; n = 0–3, 15) have been employed as catalysts and/or catalyst precursors for thermal hydrogenation and isomerization reactions of 1-octene under moderate reaction conditions (1 atm at 70°C or below). In the hydrogenation reaction the system Ru3(CO)12/15CH3CN showed the highest activity, with turnover numbers up to 1000. For this system the kinetics indicated that the hydrogenation occurs via a lower nuclearity catalytic species formed by fragmentation of the mother cluster. On the other hand the isomerization reaction occurs, after a 10–20 min induction period, by higher-nuclearity catalytic species. The isomerization gave trans-2-octene only, and none of the cis-isomer. The effects of other factors on the rates of hydrogenation and isomerization reactions are described.

Hikmat S. Hilal's picture

Poly(Siloxane)-Supported Decacarbonyldimanganese(0) Catalyst for Terminal Olefin Hydrosilylation Reactions: The Effect of The Support on The Catalyst Selectivity, Activity and Stability

Journal Title, Volume, Page: 
Journal of Molecular Catalysis A: Chemical Volume 144, Issue 1, 22 July 1999, Pages 47-59
Year of Publication: 
1999
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
Mohammad A. Suleiman
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Waheed J. 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
Moayyad M. Masoud
Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine
Preferred Abstract (Original): 

A new class of supported carbonyl manganese catalyst was prepared by treating the dimeric decacarbonyldimanganese(0), Mn2(CO)10, with insoluble aminated poly(siloxane) surface. Solid state FT-IR spectra indicated that the supported catalyst is a dimeric complex that is substituted with two amine ligands, one at each Mn atom. The supported manganese complex was investigated as catalyst for the hydrosilylation reaction of terminal olefins. Contrary to the homogeneous Mn2(CO)10 catalytic system, the supported manganese complex was completely selective toward the hydrosilylation reaction with no detectable olefin isomerization or other side-reaction products. Furthermore, the catalyst was selective to produce the linear hydrosilylation product rather than the branched one. No lowering in catalyst activity due to the support was observed. A good proportion of the catalyst activity after separation and reuse was retained for at least four times. Highly reproducible catalytic activity measurements were obtained with catalytic samples taken from same prepared batch. Different prepared batches showed lower reproducibility. The effect of different reaction parameters, such as the solvent effect, the temperature effect, the concentration effect and the added-ligand effect have also been studied. Laine's kinetic studies indicated that the cluster remained intact during the reaction.

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