Bassam El Ali | King Fahd University of Petroleum and Minerals (original) (raw)

Papers by Bassam El Ali

Research paper thumbnail of Palladium (II)‐catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity controlled by the nucleophiles

Applied Organometallic …, 2010

... Suleiman, R., Tijani, J. and El Ali, B. (2010), Palladium(II)-catalyzed catalytic aminocarbon... more ... Suleiman, R., Tijani, J. and El Ali, B. (2010), Palladium(II)-catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity ... Correspondence: Bassam El Ali, King Fahd ... 3 -], 2.31 (m, 2H, NCH 2 CH 2 ), 3.28 (t, 2 H, NCH 2 , J = 6.4 Hz), 5.56 (s, 1 H ...

Research paper thumbnail of Catalytic and regioselective synthesis of gem- or trans-?,?-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

Applied Organometallic Chemistry, 2003

The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfu... more The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc)2 and a suitable bidentate phosphine ligand. The reaction led mainly to gem-α,β-unsaturated amides (3) with Pd(OAc)2/1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc)2/1,4-bis(diphenylphosphino)butane/H2/CO in CH2Cl2 as a solvent affords trans-α,β-unsaturated amides (4) as the major product. Copyright © 2003 John Wiley & Sons, Ltd.

Research paper thumbnail of Palladium(II)-catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity controlled by the nucleophiles

Applied Organometallic Chemistry, 2009

The aminocarbonylation and alkoxycarbonylation reactions of terminal alkynes took place smoothly ... more The aminocarbonylation and alkoxycarbonylation reactions of terminal alkynes took place smoothly and efficiently using a catalyst system Pd(OAc)2–dppb–p-TsOHCH3CNCO under relatively mild experimental conditions. The catalytic system was tested and optimized using two different nucleophiles: alcohols and amines. Phenylacetylene (1a) was considered as an alkyne along with diisobutylamine (2b1) and methanol (2c1) as nucleophiles. The results showed significant differences in the conversion of 1a and in the selectivity towards the gem or trans unsaturated esters or amides with these nucleophiles. The effects of the type of palladium catalysts, the type of ligands, the amount of dppb and the solvents were carefully studied. With diisobutylamine (2b1), excellent regioselectivity towards the 2-acrylamides (gem isomer, 3ab1) was almost always observed, while trans-α,β-unsaturated esters 4ac1 was the predominant product with methanol (2c1) as a nucleophile. This remarkable sensitivity in the selectivity of the reaction indicates two different possible mechanistic pathways for these carbonylation reactions. Copyright © 2009 John Wiley & Sons, Ltd.

Research paper thumbnail of Rh 6(CO) 16-H 3PW 12O 40-catalyzed one pot hydroformylation–cyclotrimerization of cyclohexene and cyclopentene into 2,4,6-trisubstituted-1,3,5-trioxanes

Journal of Molecular Catalysis A-chemical, 2003

ABSTRACT

Research paper thumbnail of Catalytic and selective synthesis of lactones and bis-lactones by palladium acetate/1,4-bis(diphenylphosphino)butane system under syngas conditions

Journal of Molecular Catalysis A-chemical, 2003

made a great contribution to catalysis and organometallic chemistry. We have learned a great deal... more made a great contribution to catalysis and organometallic chemistry. We have learned a great deal from him

Research paper thumbnail of Synthesis of bislactones catalysed by a Pd-dppb system

Applied Organometallic Chemistry, 2000

ABSTRACT

Research paper thumbnail of Ultranox626 as a selective ligand in rhodium-catalyzed hydroformylation–acetalization of allylbenzene derivatives

Reaction Kinetics, Mechanisms and Catalysis

Ultranox626 as a diphosphite ligand showed high selectivity and good yields when used with Rh(CO)... more Ultranox626 as a diphosphite ligand showed high selectivity and good yields when used with Rh(CO)2(acac) as a catalyst precursor in the hydroformylation of allylbenzene derivatives producing aldehydes, and also in the one-pot hydroformylation–acetalization forming acetals. These reactions proceed smoothly and effectively to produce the linear aldehydes or acetals with high selectivity. The recycling of the rhodium catalyst was carried out after the careful screening and optimization of the reaction conditions in order to maximize the conversion and the selectivity of the reactions.

Research paper thumbnail of Rh(I) or Rh(III) supported on MCM-41-catalyzed selective hydroformylation–acetalization of aryl alkenes: Effect of the additives

Applied Catalysis A-general, 2006

Rh(III) impregnated on mesoporous supports such as MCM-41 have demonstrated a very high catalytic... more Rh(III) impregnated on mesoporous supports such as MCM-41 have demonstrated a very high catalytic activity in the production of acetals under the hydroformylation conditions of alkenes. The one pot process that combines hydroformylation and acetalization processes leading to acetals as major products was carefully studied. R(I) supported catalysts combined with the heteropolyacid H 3 PW 12 O 40 showed high catalytic activity towards the formation of acetals. However, Rh(III) supported catalysts were much more active in the absence of any additive. The addition of P(OPh) 3 increased significantly the selectivity of the reaction towards the branched acetals. The effects of the addition of different types of phosphine and phosphite ligands were studied. #

Research paper thumbnail of ChemInform Abstract: Palladium(II) Acetate Catalyzed Efficient Synthesis of N-Aryl-α,β-unsaturated Amides via Carbonylative Addition of Aniline Derivatives to Aromatic Alkynes

Cheminform, 2010

For Abstract see ChemInform Abstract in Full Text.

Research paper thumbnail of Pd(II)—dppb and syngas catalyze regioselective hydroesterification of terminal alkynes under neutral conditions

Tetrahedron Letters, 2001

Palladium(II) regioselectively catalyzes the hydroesterification of terminal alkynes under syngas... more Palladium(II) regioselectively catalyzes the hydroesterification of terminal alkynes under syngas forming a,b-unsaturated esters 3 and 4 in excellent chemical yields under neutral conditions. The high selectivity for the linear ester 4 was obtained with a catalytic system that includes Pd(II), 1,4-bis(diphenylphosphino)butane (dppb) and CO/H 2 in CH 2 Cl 2 as solvent. The control of the regioselectivity depends strongly upon the type of ligand, the solvent and the use of the syngas mixture.

Research paper thumbnail of Total regioselective control of the carbonylative coupling of 1-heptyne with aniline and N-methyl aniline catalyzed by palladium(II) and phosphine ligand

Journal of Molecular Catalysis A-chemical, 2002

The carbonylative coupling of 1-heptyne (1a) with aniline (2a) has been successfully achieved in ... more The carbonylative coupling of 1-heptyne (1a) with aniline (2a) has been successfully achieved in the presence of Pd(OAc) 2 and a suitable bidentate phosphine ligand and solvent. The gem-␣,␤-unsaturated amide (3aa) was formed as a predominant product in the presence of the catalytic system Pd(OAc) 2 /1,3-bis(diphenylphosphino)propane (dppp)/p-toluenesulfonic acid (p-TsOH)/CO in THF as a solvent. While the use Pd(OAc) 2 and 1,4-bis(diphenylphosphino)butane (dppb), under syngas (CO/H 2 ) conditions and in CH 2 Cl 2 as a solvent, affords the trans-␣,␤-unsaturated amide (4aa) as the major product. A minor cyclic product (5aa) was formed via the double carbonylation reaction. The regioselective carbonylative coupling reaction was also successfully applied to N-methyl aniline (2b) with 1-heptyne (1a) producing excellent yields of tertiary unsaturated amides.

Research paper thumbnail of Mixed-ligand platinum and palladium complexes based on dinitrogen chelating ligands and a pyridine bearing the nitronylnitroxide radical

Inorganic Chemistry Communications, 2007

Novel cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-d... more Novel cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-dimethyl-1,10-phenanthroline and 2,2 0 -bipyridine with a pyridine bearing the nitronylnitroxide radical are reported. The synthesis, X-ray crystal structures and magnetic properties of the two complexes [Pd(4,7-dimethyl-1,10-phenanthroline)(NIT-pPy) 2 ](PF 6 ) 2 . DMF and [Pt(2,2 0 -bipyridine-N,N 0 )(NIT-pPy) 2 ](PF 6 ) 2 AE 0.25H 2 O, (where NIT-pPy = 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) are described. The two metal complexes show a strained square planar geometry. Short intermolecular contacts take place through the nitroxide groups and weak intermolecular antiferromagnetic interactions are dominant at low temperature.

Research paper thumbnail of Catalytic and regioselective synthesis of gem- or trans-?,?-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

Applied Organometallic Chemistry, 2003

The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfu... more The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc)2 and a suitable bidentate phosphine ligand. The reaction led mainly to gem-α,β-unsaturated amides (3) with Pd(OAc)2/1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc)2/1,4-bis(diphenylphosphino)butane/H2/CO in CH2Cl2 as a solvent affords trans-α,β-unsaturated amides (4) as the major product. Copyright © 2003 John Wiley & Sons, Ltd.

Research paper thumbnail of Metal-Dependent Ferro- Versus Antiferromagnetic Interactions in Molecular Crystals of Square Planar {M(II) Imino-Nitroxide Radical} Complexes (M = Pt, Pd

Inorganic Chemistry, 2003

The synthesis and structural, spectral, and magnetic characterizations of two new complexes of fo... more The synthesis and structural, spectral, and magnetic characterizations of two new complexes of formula [Pt(IM 2 -Py)Cl 2 ] (A) and [Pd(IM 2 Py)Cl 2 ] (B) are reported. IM 2 Py stands for the imino-nitroxide radical ligand 2-(ortho-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl. Their crystal structures were solved at room temperature and at 120 K revealing structural phase transitions from pseudo-orthorhombic to monoclinic systems for the two compounds which remain isostructural in the whole temperature range explored. Structural parameters for A: [10.168(4)] Å, c ) 10.357(3) [17.623(6)] Å, ) 90.732-(13)°[95.940(2)]°, Z ) 4 [4]. Structural parameters for B: T ) 293 K [120 K], monoclinic (P2 1 /n) [P2 1 /c], a ) 7.900(3) [7.9730(2)] Å, b ) 17.907(9) [10.1806(3)] Å, c ) 10.299(3) [17.7171(4)] Å, ) 90.524(14)°[95.747(2)]°, Z ) 4 [4]. In both complexes, the metal coordination is essentially planar. The average Pt−N, Pt−Cl and Pd−N, Pd−Cl bond lengths are 1.996(6) [1.88], 2.295(2) [2.248(8)] Å and 2.015(7) [2.029(8)], 2.287(3) [2.294 ] Å, respectively. The solid state structure is characterized by a pairlike molecular packing stacked in columns parallel to the a axis; this dimer character is reinforced at low temperature. Despite their structural similarity, the investigation of the magnetic properties revealed that dominant ferromagnetic interactions govern the behavior of the Pt derivative A, whereas antiferromagnetic interactions take place for the Pd compound B. A rationalization for this rather intriguing difference is proposed in light of the spin population deduced from density functional theory calculations. The electronic absorption spectra of A and B present structured absorption bands in the visible which are attributed to MLCT transitions. Both compounds are nonluminescent at room temperature. However, a weak emission is detected for A in butyronitrile glasses at 77 K, indicating that the MLCT excited state is strongly quenched at low temperature.

Research paper thumbnail of Hydroformylation of alkyl alkenes catalyzed by rhodium supported on MCM-41: The effect of H 3PW 12O 40 on the catalytic activity and recycling

Journal of Molecular Catalysis A-chemical, 2006

Heteropolyacids impregnated with rhodium(I) or (III) complexes were prepared and used as supporte... more Heteropolyacids impregnated with rhodium(I) or (III) complexes were prepared and used as supported catalysts in the hydroformylation of alkyl alkenes. Two general types of catalysts were prepared and tested: rhodium(I) or (III) in the presence and in the absence of the heteropolyacid H 3 PW 12 O 40 , 25H 2 O (adopted as HPW 12 ) supported on MCM-41 (30Å). 1-Octene was chosen as a model substrate. Different types of supported catalysts were tested in the hydroformylation of 1-octene and other alkyl alkenes. The effects of the temperature and the type of solvent on the reaction were studied. The results showed that the supported catalysts containing the heteropolyacid H 3 PW 12 O 40 , 25H 2 O (HPW 12 ) along with rhodium(I) or (III) gave higher catalytic activity. In addition, the recycling of the supported catalysts was studied and the results showed again the important effect of the presence of HPW 12 on the recycling of the rhodium catalysts.

Research paper thumbnail of Mixed-ligand complexes of copper(I) with diimines and phosphines: Effective catalysts for the coupling of phenylacetylene with halobenzene

Polyhedron, 2009

New copper (I) mixed-ligand complexes 1–4 of the formula Cu (N–N) PR3X, where N–N= 1, 10-phenanth... more New copper (I) mixed-ligand complexes 1–4 of the formula Cu (N–N) PR3X, where N–N= 1, 10-phenanthroline (phen), 2, 2′-bipyridine (bpy), 5, 5′-dimethyl-2, 2′-bipyridine (5, 5′ dimbpy) and PR3= tricyclohexylphosphine, tris (2-cyanoethyl) phosphine and ...

Research paper thumbnail of ChemInform Abstract: Palladium(II)-Catalyzed Catalytic Aminocarbonylation and Alkoxycarbonylation of Terminal Alkynes: Regioselectivity Controlled by the Nucleophiles

Cheminform, 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of ChemInform Abstract: Pd(II)-dppb and Syngas Catalyze Regioselective Hydroesterification of Terminal Alkynes under Neutral Conditions

Cheminform, 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of H 3+ n PMo 12− n V n O 40-catalyzed selective oxidation of benzoins to benzils or aldehydes and esters by dioxygen

Journal of Molecular Catalysis A-chemical, 2001

... using the heteropolyacid H 3+n PMo 12−n V n O 40 (HPA-2), as a catalyst affording carboxylic ... more ... using the heteropolyacid H 3+n PMo 12−n V n O 40 (HPA-2), as a catalyst affording carboxylic acid derivatives in high yields [3]. On the other hand, cyclic ketones in alcohols were oxidatively cleaved in the presence of stoichiometric amount of oxovanadium(V), VO(OEt)Cl 2 and ...

Research paper thumbnail of Palladium(II) acetate catalyzed efficient synthesis ofN-aryl-?,?-unsaturated amidesvia carbonylative addition of aniline derivatives to aromatic alkynes

Applied Organometallic Chemistry, 2002

A series of new N-aryl-α,β-disubstituted amides (gem or E1; trans or E2) were synthesized in good... more A series of new N-aryl-α,β-disubstituted amides (gem or E1; trans or E2) were synthesized in good yields by carbonylative addition of aniline derivatives 1a–f to aromatic alkynes 2a,b catalyzed by Pd(OAc)2 and 1,3-bis(diphenylphosphino)propane. The catalytic synthesis of tertiary α,β-unsaturated amides was also successfully achieved. Traces of products were observed in the absence of p-toluenesulfonic acid used as an additive. The reaction is sensitive to the type of phosphine ligand and solvent. Copyright © 2002 John Wiley & Sons, Ltd.

Research paper thumbnail of Palladium (II)‐catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity controlled by the nucleophiles

Applied Organometallic …, 2010

... Suleiman, R., Tijani, J. and El Ali, B. (2010), Palladium(II)-catalyzed catalytic aminocarbon... more ... Suleiman, R., Tijani, J. and El Ali, B. (2010), Palladium(II)-catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity ... Correspondence: Bassam El Ali, King Fahd ... 3 -], 2.31 (m, 2H, NCH 2 CH 2 ), 3.28 (t, 2 H, NCH 2 , J = 6.4 Hz), 5.56 (s, 1 H ...

Research paper thumbnail of Catalytic and regioselective synthesis of gem- or trans-?,?-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

Applied Organometallic Chemistry, 2003

The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfu... more The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc)2 and a suitable bidentate phosphine ligand. The reaction led mainly to gem-α,β-unsaturated amides (3) with Pd(OAc)2/1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc)2/1,4-bis(diphenylphosphino)butane/H2/CO in CH2Cl2 as a solvent affords trans-α,β-unsaturated amides (4) as the major product. Copyright © 2003 John Wiley & Sons, Ltd.

Research paper thumbnail of Palladium(II)-catalyzed catalytic aminocarbonylation and alkoxycarbonylation of terminal alkynes: regioselectivity controlled by the nucleophiles

Applied Organometallic Chemistry, 2009

The aminocarbonylation and alkoxycarbonylation reactions of terminal alkynes took place smoothly ... more The aminocarbonylation and alkoxycarbonylation reactions of terminal alkynes took place smoothly and efficiently using a catalyst system Pd(OAc)2–dppb–p-TsOHCH3CNCO under relatively mild experimental conditions. The catalytic system was tested and optimized using two different nucleophiles: alcohols and amines. Phenylacetylene (1a) was considered as an alkyne along with diisobutylamine (2b1) and methanol (2c1) as nucleophiles. The results showed significant differences in the conversion of 1a and in the selectivity towards the gem or trans unsaturated esters or amides with these nucleophiles. The effects of the type of palladium catalysts, the type of ligands, the amount of dppb and the solvents were carefully studied. With diisobutylamine (2b1), excellent regioselectivity towards the 2-acrylamides (gem isomer, 3ab1) was almost always observed, while trans-α,β-unsaturated esters 4ac1 was the predominant product with methanol (2c1) as a nucleophile. This remarkable sensitivity in the selectivity of the reaction indicates two different possible mechanistic pathways for these carbonylation reactions. Copyright © 2009 John Wiley & Sons, Ltd.

Research paper thumbnail of Rh 6(CO) 16-H 3PW 12O 40-catalyzed one pot hydroformylation–cyclotrimerization of cyclohexene and cyclopentene into 2,4,6-trisubstituted-1,3,5-trioxanes

Journal of Molecular Catalysis A-chemical, 2003

ABSTRACT

Research paper thumbnail of Catalytic and selective synthesis of lactones and bis-lactones by palladium acetate/1,4-bis(diphenylphosphino)butane system under syngas conditions

Journal of Molecular Catalysis A-chemical, 2003

made a great contribution to catalysis and organometallic chemistry. We have learned a great deal... more made a great contribution to catalysis and organometallic chemistry. We have learned a great deal from him

Research paper thumbnail of Synthesis of bislactones catalysed by a Pd-dppb system

Applied Organometallic Chemistry, 2000

ABSTRACT

Research paper thumbnail of Ultranox626 as a selective ligand in rhodium-catalyzed hydroformylation–acetalization of allylbenzene derivatives

Reaction Kinetics, Mechanisms and Catalysis

Ultranox626 as a diphosphite ligand showed high selectivity and good yields when used with Rh(CO)... more Ultranox626 as a diphosphite ligand showed high selectivity and good yields when used with Rh(CO)2(acac) as a catalyst precursor in the hydroformylation of allylbenzene derivatives producing aldehydes, and also in the one-pot hydroformylation–acetalization forming acetals. These reactions proceed smoothly and effectively to produce the linear aldehydes or acetals with high selectivity. The recycling of the rhodium catalyst was carried out after the careful screening and optimization of the reaction conditions in order to maximize the conversion and the selectivity of the reactions.

Research paper thumbnail of Rh(I) or Rh(III) supported on MCM-41-catalyzed selective hydroformylation–acetalization of aryl alkenes: Effect of the additives

Applied Catalysis A-general, 2006

Rh(III) impregnated on mesoporous supports such as MCM-41 have demonstrated a very high catalytic... more Rh(III) impregnated on mesoporous supports such as MCM-41 have demonstrated a very high catalytic activity in the production of acetals under the hydroformylation conditions of alkenes. The one pot process that combines hydroformylation and acetalization processes leading to acetals as major products was carefully studied. R(I) supported catalysts combined with the heteropolyacid H 3 PW 12 O 40 showed high catalytic activity towards the formation of acetals. However, Rh(III) supported catalysts were much more active in the absence of any additive. The addition of P(OPh) 3 increased significantly the selectivity of the reaction towards the branched acetals. The effects of the addition of different types of phosphine and phosphite ligands were studied. #

Research paper thumbnail of ChemInform Abstract: Palladium(II) Acetate Catalyzed Efficient Synthesis of N-Aryl-α,β-unsaturated Amides via Carbonylative Addition of Aniline Derivatives to Aromatic Alkynes

Cheminform, 2010

For Abstract see ChemInform Abstract in Full Text.

Research paper thumbnail of Pd(II)—dppb and syngas catalyze regioselective hydroesterification of terminal alkynes under neutral conditions

Tetrahedron Letters, 2001

Palladium(II) regioselectively catalyzes the hydroesterification of terminal alkynes under syngas... more Palladium(II) regioselectively catalyzes the hydroesterification of terminal alkynes under syngas forming a,b-unsaturated esters 3 and 4 in excellent chemical yields under neutral conditions. The high selectivity for the linear ester 4 was obtained with a catalytic system that includes Pd(II), 1,4-bis(diphenylphosphino)butane (dppb) and CO/H 2 in CH 2 Cl 2 as solvent. The control of the regioselectivity depends strongly upon the type of ligand, the solvent and the use of the syngas mixture.

Research paper thumbnail of Total regioselective control of the carbonylative coupling of 1-heptyne with aniline and N-methyl aniline catalyzed by palladium(II) and phosphine ligand

Journal of Molecular Catalysis A-chemical, 2002

The carbonylative coupling of 1-heptyne (1a) with aniline (2a) has been successfully achieved in ... more The carbonylative coupling of 1-heptyne (1a) with aniline (2a) has been successfully achieved in the presence of Pd(OAc) 2 and a suitable bidentate phosphine ligand and solvent. The gem-␣,␤-unsaturated amide (3aa) was formed as a predominant product in the presence of the catalytic system Pd(OAc) 2 /1,3-bis(diphenylphosphino)propane (dppp)/p-toluenesulfonic acid (p-TsOH)/CO in THF as a solvent. While the use Pd(OAc) 2 and 1,4-bis(diphenylphosphino)butane (dppb), under syngas (CO/H 2 ) conditions and in CH 2 Cl 2 as a solvent, affords the trans-␣,␤-unsaturated amide (4aa) as the major product. A minor cyclic product (5aa) was formed via the double carbonylation reaction. The regioselective carbonylative coupling reaction was also successfully applied to N-methyl aniline (2b) with 1-heptyne (1a) producing excellent yields of tertiary unsaturated amides.

Research paper thumbnail of Mixed-ligand platinum and palladium complexes based on dinitrogen chelating ligands and a pyridine bearing the nitronylnitroxide radical

Inorganic Chemistry Communications, 2007

Novel cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-d... more Novel cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-dimethyl-1,10-phenanthroline and 2,2 0 -bipyridine with a pyridine bearing the nitronylnitroxide radical are reported. The synthesis, X-ray crystal structures and magnetic properties of the two complexes [Pd(4,7-dimethyl-1,10-phenanthroline)(NIT-pPy) 2 ](PF 6 ) 2 . DMF and [Pt(2,2 0 -bipyridine-N,N 0 )(NIT-pPy) 2 ](PF 6 ) 2 AE 0.25H 2 O, (where NIT-pPy = 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) are described. The two metal complexes show a strained square planar geometry. Short intermolecular contacts take place through the nitroxide groups and weak intermolecular antiferromagnetic interactions are dominant at low temperature.

Research paper thumbnail of Catalytic and regioselective synthesis of gem- or trans-?,?-unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

Applied Organometallic Chemistry, 2003

The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfu... more The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc)2 and a suitable bidentate phosphine ligand. The reaction led mainly to gem-α,β-unsaturated amides (3) with Pd(OAc)2/1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc)2/1,4-bis(diphenylphosphino)butane/H2/CO in CH2Cl2 as a solvent affords trans-α,β-unsaturated amides (4) as the major product. Copyright © 2003 John Wiley & Sons, Ltd.

Research paper thumbnail of Metal-Dependent Ferro- Versus Antiferromagnetic Interactions in Molecular Crystals of Square Planar {M(II) Imino-Nitroxide Radical} Complexes (M = Pt, Pd

Inorganic Chemistry, 2003

The synthesis and structural, spectral, and magnetic characterizations of two new complexes of fo... more The synthesis and structural, spectral, and magnetic characterizations of two new complexes of formula [Pt(IM 2 -Py)Cl 2 ] (A) and [Pd(IM 2 Py)Cl 2 ] (B) are reported. IM 2 Py stands for the imino-nitroxide radical ligand 2-(ortho-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl. Their crystal structures were solved at room temperature and at 120 K revealing structural phase transitions from pseudo-orthorhombic to monoclinic systems for the two compounds which remain isostructural in the whole temperature range explored. Structural parameters for A: [10.168(4)] Å, c ) 10.357(3) [17.623(6)] Å, ) 90.732-(13)°[95.940(2)]°, Z ) 4 [4]. Structural parameters for B: T ) 293 K [120 K], monoclinic (P2 1 /n) [P2 1 /c], a ) 7.900(3) [7.9730(2)] Å, b ) 17.907(9) [10.1806(3)] Å, c ) 10.299(3) [17.7171(4)] Å, ) 90.524(14)°[95.747(2)]°, Z ) 4 [4]. In both complexes, the metal coordination is essentially planar. The average Pt−N, Pt−Cl and Pd−N, Pd−Cl bond lengths are 1.996(6) [1.88], 2.295(2) [2.248(8)] Å and 2.015(7) [2.029(8)], 2.287(3) [2.294 ] Å, respectively. The solid state structure is characterized by a pairlike molecular packing stacked in columns parallel to the a axis; this dimer character is reinforced at low temperature. Despite their structural similarity, the investigation of the magnetic properties revealed that dominant ferromagnetic interactions govern the behavior of the Pt derivative A, whereas antiferromagnetic interactions take place for the Pd compound B. A rationalization for this rather intriguing difference is proposed in light of the spin population deduced from density functional theory calculations. The electronic absorption spectra of A and B present structured absorption bands in the visible which are attributed to MLCT transitions. Both compounds are nonluminescent at room temperature. However, a weak emission is detected for A in butyronitrile glasses at 77 K, indicating that the MLCT excited state is strongly quenched at low temperature.

Research paper thumbnail of Hydroformylation of alkyl alkenes catalyzed by rhodium supported on MCM-41: The effect of H 3PW 12O 40 on the catalytic activity and recycling

Journal of Molecular Catalysis A-chemical, 2006

Heteropolyacids impregnated with rhodium(I) or (III) complexes were prepared and used as supporte... more Heteropolyacids impregnated with rhodium(I) or (III) complexes were prepared and used as supported catalysts in the hydroformylation of alkyl alkenes. Two general types of catalysts were prepared and tested: rhodium(I) or (III) in the presence and in the absence of the heteropolyacid H 3 PW 12 O 40 , 25H 2 O (adopted as HPW 12 ) supported on MCM-41 (30Å). 1-Octene was chosen as a model substrate. Different types of supported catalysts were tested in the hydroformylation of 1-octene and other alkyl alkenes. The effects of the temperature and the type of solvent on the reaction were studied. The results showed that the supported catalysts containing the heteropolyacid H 3 PW 12 O 40 , 25H 2 O (HPW 12 ) along with rhodium(I) or (III) gave higher catalytic activity. In addition, the recycling of the supported catalysts was studied and the results showed again the important effect of the presence of HPW 12 on the recycling of the rhodium catalysts.

Research paper thumbnail of Mixed-ligand complexes of copper(I) with diimines and phosphines: Effective catalysts for the coupling of phenylacetylene with halobenzene

Polyhedron, 2009

New copper (I) mixed-ligand complexes 1–4 of the formula Cu (N–N) PR3X, where N–N= 1, 10-phenanth... more New copper (I) mixed-ligand complexes 1–4 of the formula Cu (N–N) PR3X, where N–N= 1, 10-phenanthroline (phen), 2, 2′-bipyridine (bpy), 5, 5′-dimethyl-2, 2′-bipyridine (5, 5′ dimbpy) and PR3= tricyclohexylphosphine, tris (2-cyanoethyl) phosphine and ...

Research paper thumbnail of ChemInform Abstract: Palladium(II)-Catalyzed Catalytic Aminocarbonylation and Alkoxycarbonylation of Terminal Alkynes: Regioselectivity Controlled by the Nucleophiles

Cheminform, 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of ChemInform Abstract: Pd(II)-dppb and Syngas Catalyze Regioselective Hydroesterification of Terminal Alkynes under Neutral Conditions

Cheminform, 2010

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was e... more ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Research paper thumbnail of H 3+ n PMo 12− n V n O 40-catalyzed selective oxidation of benzoins to benzils or aldehydes and esters by dioxygen

Journal of Molecular Catalysis A-chemical, 2001

... using the heteropolyacid H 3+n PMo 12−n V n O 40 (HPA-2), as a catalyst affording carboxylic ... more ... using the heteropolyacid H 3+n PMo 12−n V n O 40 (HPA-2), as a catalyst affording carboxylic acid derivatives in high yields [3]. On the other hand, cyclic ketones in alcohols were oxidatively cleaved in the presence of stoichiometric amount of oxovanadium(V), VO(OEt)Cl 2 and ...

Research paper thumbnail of Palladium(II) acetate catalyzed efficient synthesis ofN-aryl-?,?-unsaturated amidesvia carbonylative addition of aniline derivatives to aromatic alkynes

Applied Organometallic Chemistry, 2002

A series of new N-aryl-α,β-disubstituted amides (gem or E1; trans or E2) were synthesized in good... more A series of new N-aryl-α,β-disubstituted amides (gem or E1; trans or E2) were synthesized in good yields by carbonylative addition of aniline derivatives 1a–f to aromatic alkynes 2a,b catalyzed by Pd(OAc)2 and 1,3-bis(diphenylphosphino)propane. The catalytic synthesis of tertiary α,β-unsaturated amides was also successfully achieved. Traces of products were observed in the absence of p-toluenesulfonic acid used as an additive. The reaction is sensitive to the type of phosphine ligand and solvent. Copyright © 2002 John Wiley & Sons, Ltd.