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Papers by Anna Trzeciak
Summary. Palladium(II) complexes of the general formula PdCl2 (PR3)2 with PR3 = { P(OPh)3}, P(O... more Summary. Palladium(II) complexes of the general formula PdCl2 (PR3)2 with PR3 = { P(OPh)3}, P(O-4-MeC6H4)3, P(O-2-MeC6H4)3, and PPh2(OBu) were reduced by NEt3 in chloroform or benzene to Pd(0) complexes Pd(PR3)4 and Pd(PR3)x(NEt3) 4−x . The same reaction performed in the presence of air gave CH3CHO or CH3CH2CHO when NPr3 was used instead of NEt3. Pd(P(OPh)3)4 reacted with benzyl bromide affording the oxidative addition
ABSTRACT The catalytic decomposition of cumene hydroperoxide in the presence of μ3-oxotrirutheniu... more ABSTRACT The catalytic decomposition of cumene hydroperoxide in the presence of μ3-oxotriruthenium hexacarboxylate at T ⩾ 308 K has been studied. On the basis of kinetic investigations, a mechanism of hydroperoxide decomposition is suggested; the influence of the donor—acceptor properties of the solvent is also demonstrated. The reaction products are cumyl alcohol, acetophenone and dioxygen in proportions that depend on the initial hydroxperoxide concentration. From the results of IR and electornic absorption measurements, it was shown that the ruthenium complex does not change during the reaction.
Journal of Molecular Catalysis A-chemical, 1999
A catalytic system containing [Rh(acac)(CO)2] and water soluble phosphine PNS (PNSPh2PCH2CH2CONH... more A catalytic system containing [Rh(acac)(CO)2] and water soluble phosphine PNS (PNSPh2PCH2CH2CONHC(CH3)2CH2SO3Li) was used for the hydrogenation and hydroformylation of C4 unsaturated alcohols: 1-buten-3-ol (CH2=CHCH(CH3)OH) (1), 2-methyl-2-propen-1-ol (CH2C(CH3)CH2OH) (2) and 2-buten-1-ol (CH3CHCHCH2OH) (3) in water. The most reactive substrate, (1), with a terminal double bond, is hydrogenated at 313 K and 0.1 MPa of H2 pressure giving 92% of 2-methyl-propanol after
Acta Crystallographica Section C Crystal Structure Communications, 2006
The title compound, [Pd2(C12H10O3P)2Cl2(C12H11O3P)2], consists of a dinuclear mu-chloro-bridged p... more The title compound, [Pd2(C12H10O3P)2Cl2(C12H11O3P)2], consists of a dinuclear mu-chloro-bridged palladium unit with two diphenoxyphosphinite groups per Pd atom, linked together by a hydrogen bond. The asymmetric unit contains one half of the molecule, with the other half generated by an inversion centre. The geometry around the P atoms may be described as distorted tetrahedral. Adjacent molecules of the complex are linked by weak C-H...O and C-H...Cl hydrogen bonds. The structure is additionally stabilized by pi-pi stacking interactions between the aryl rings. These interactions form a herring-bone pattern in the crystal structure.
New Journal of Chemistry, 2008
ABSTRACT Cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) in the form of gel-t... more ABSTRACT Cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) in the form of gel-type beads was used to encapsulate Pd(0)nanoparticles 4–15 nm in diameter and applied as a new, reusable catalyst for the Suzuki–Miyaura cross-coupling reaction of 2- and 4-bromotoluene with phenylboronic acid. It was found that the precatalyst preparation methodology strongly influenced its catalytic activity. The best results (100% yield of the product) were obtained when GMA-CHDA was first treated with hydrazine (reducing agent for Pd(II)) and next with PdCl2 solution. The new catalyst acts heterogeneously, and the post-reaction solution after catalyst separation is not catalytically active, suggesting that there is no leaching.
Journal of Organometallic Chemistry, 1999
The novel rhodium complexes with the bidentate PO ligand (PO = OC 6 H 4 PPh 2 − ) of the form Rh(... more The novel rhodium complexes with the bidentate PO ligand (PO = OC 6 H 4 PPh 2 − ) of the form Rh(PO)(CO)L (L a =POH= HOC 6 H 4 PPh 2 (1), PPh 3 (2), P(NC 4 H 4 ) 3 (4), PPh 2 (NC 4 H 4 ) (6)) and Rh(PO)L 2 (L b = P(OPh) 3 (3), P(NC 4 H 4 ) 3 (5)) were obtained by ligand exchange in Rh(b-diketone)(CO) 2 , Rh(b-diketone)(CO)L and Rh(b-diketone)L 2 complexes. All complexes of the Rh(PO)(CO)L a type exist in solution as isomers with both phosphorus atoms in the trans position as was shown by 31 P{ 1 H}-NMR. The trans influence of the phosphorus atom of a bidentate PO ligand is stronger than that of oxygen atom, which is manifested by the differences of Rh-P bonds in (2) (2.283(1) and 2.327(1) Å ) and of Rh -P (phosphite) bonds in (3) (2.233(2) and 2.139(2) Å ). The complexes (1) and (2) used alone or with an excess of free phosphine (POH, PPh 3 , P(NC 4 H 4 ) 3 ) are not active in hexen-1-e hydroformylation at 1 MPa CO/H 2 =1 and at 353 K. The lack of catalytic activity is explained by the extremely high stability of the chelate (PO) ring which does not allow the formation of the active form of the catalyst. In contrast, the complex (3) used alone as the catalyst precursor produces 54 and 72.9% of aldehydes when used with a six-fold excess of P(OPh) 3 . Complex (1) modified with P(OPh) 3 catalyses hexen-1-e hydroformylation with a 73.6 -84.6% yield of aldehydes. Under hydroformylation reaction conditions, the PO ligand is removed from the coordination sphere of (1) and complexes of the form HRh(CO){P(OPh) 3 } 3 and HRh{P(OPh) 3 } 4 are formed.
Journal of Organometallic Chemistry, 2001
The substitution of CO ligand in rhodium(I) β-ketoiminato complexes Rh(R1{O,N}R2)(CO)2 ({O,N}=R1... more The substitution of CO ligand in rhodium(I) β-ketoiminato complexes Rh(R1{O,N}R2)(CO)2 ({O,N}=R1C(O)CHC(NH)R2; R1, R2=CF3, Me, CMe3 in several combinations) by phosphorus ligands PZ3 (PZ3=PCy3, PPh3, P(OPh)3, P(NC4H4)3) leads to Rh(R1{O,N}R2)(CO)(PZ3) complexes characterised by 31P{1H}-NMR and X-ray methods. The stronger σ-donor PZ3 ligands (PZ3=PCy3, PPh3) substitute almost exclusively the CO group trans to N, forming P-trans-to-N isomers. The complexes Rh(CF3{O,N}Me)(CO)(PCy3) (II), Rh(CF3{O,N}CMe3)(CO)(PCy3) (III), Rh(CF3{O,N}Me)(CO)(PPh3) (IV) and Rh(CF3{O,N}CMe)(CO)(PPh3) (V) are of a square-planar geometry with a slight tetrahedral distortion around the rhodium atom in II, III and V. The Rh-P(PCy3) bonds are slightly longer than the Rh-P(PPh3) bonds. The reaction of stoichiometric amounts of the less basic P(OPh)3 or P(NC4H4)3 ligands leads to the formation of both isomers of the Rh(R1{O,N}R2)(CO)(P(OPh)3) or Rh(R1{O,N}R2)(CO)(P(NC4H4)3) complex in comparable yields. The Rh-P(P(OPh)3) distance (2.195(2) Å) in the isomer of Rh(CF3{O,N}CMe3)(CO)(P(OPh)3) with P(OPh)3 coordinated trans to N (VI) is ca. 0.04 Å longer than in the isomer of that complex with P(OPh)3 coordinated trans to O (VII). The CO substitution in Rh(R1{O,N}R2)(CO)2 by PZ3 ligands (PPh3, PCy3, P(OPh)3) causes the shortening of the Rh-C(CO) bond by ca. 0.04 Å compared to Rh(CF3{O,N}Me)(CO)2 (I). The more π-acceptor P(OPh)3 ligands form bis-phosphito complexes; Rh(CF3{O,N}CMe3){P(OPh)3}2 (VIII) exhibits inequivalence of the two P(OPh)3 ligands in solution (31P-NMR) as well as in solid form (X-ray).
Journal of Molecular Catalysis A: Chemical, 2004
Journal of Molecular Catalysis …, 1996
... Journal of Molecular Catalysis A: Chemical 110 (1996) 135139 JOURNAL OF MOLECULAR CATALYSIS 1... more ... Journal of Molecular Catalysis A: Chemical 110 (1996) 135139 JOURNAL OF MOLECULAR CATALYSIS 10 A: CHEMICAL New bimetallic rhodiumzirconium catalysts for homogeneous olefin hydroformylation Anna M. Trzeciak a ... [9] AM Trzeciak, M. Jon and JJ Ziolkowski, React. ...
Applied Catalysis A: General, 2010
Two palladium catalyst precursors were prepared by immobilizing PdCl2 and Pd(OAc)2 on cyclohexyld... more Two palladium catalyst precursors were prepared by immobilizing PdCl2 and Pd(OAc)2 on cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) and used in the Suzuki–Miyaura reaction (80°C, 2h) without any pre-treatment. Using the TEM, SEM, EDS, and XPS methods, we were able to characterize the Pd(0) nanoparticles formed in situ during the catalytic process. The catalyst obtained from Pd(OAc)2 (P2) contained Pd(0) nanoparticles
Catalysis Letters, 2006
Efficient cross-coupling and carbonylative coupling of terminal alkynes with aryl iodides catalyz... more Efficient cross-coupling and carbonylative coupling of terminal alkynes with aryl iodides catalyzed by PdCl 2 (P(OPh) 3 ) 2 in the presence of NEt 3 in toluene and in ionic liquids is described. In imidazolium ionic liquids, [bmim]PF 6 or [mokt]PF 6 (bmim = 1butyl-3-methyl imidazolium cation, mokt=1-methyl-3-octyl imidazolium cation) catalyst was recycled and used in four concecutive catalytic cycles with high activity. In the absence of aryl iodide the same catalytic system catalyzed head-to-tail dimerization of phenylacetylene to the 1,3-diphenyl enyne, trans-PhC CAC(Ph)@CH 2 ; with a yield of 85%.
Summary. Palladium(II) complexes of the general formula PdCl2 (PR3)2 with PR3 = { P(OPh)3}, P(O... more Summary. Palladium(II) complexes of the general formula PdCl2 (PR3)2 with PR3 = { P(OPh)3}, P(O-4-MeC6H4)3, P(O-2-MeC6H4)3, and PPh2(OBu) were reduced by NEt3 in chloroform or benzene to Pd(0) complexes Pd(PR3)4 and Pd(PR3)x(NEt3) 4−x . The same reaction performed in the presence of air gave CH3CHO or CH3CH2CHO when NPr3 was used instead of NEt3. Pd(P(OPh)3)4 reacted with benzyl bromide affording the oxidative addition
ABSTRACT The catalytic decomposition of cumene hydroperoxide in the presence of μ3-oxotrirutheniu... more ABSTRACT The catalytic decomposition of cumene hydroperoxide in the presence of μ3-oxotriruthenium hexacarboxylate at T ⩾ 308 K has been studied. On the basis of kinetic investigations, a mechanism of hydroperoxide decomposition is suggested; the influence of the donor—acceptor properties of the solvent is also demonstrated. The reaction products are cumyl alcohol, acetophenone and dioxygen in proportions that depend on the initial hydroxperoxide concentration. From the results of IR and electornic absorption measurements, it was shown that the ruthenium complex does not change during the reaction.
Journal of Molecular Catalysis A-chemical, 1999
A catalytic system containing [Rh(acac)(CO)2] and water soluble phosphine PNS (PNSPh2PCH2CH2CONH... more A catalytic system containing [Rh(acac)(CO)2] and water soluble phosphine PNS (PNSPh2PCH2CH2CONHC(CH3)2CH2SO3Li) was used for the hydrogenation and hydroformylation of C4 unsaturated alcohols: 1-buten-3-ol (CH2=CHCH(CH3)OH) (1), 2-methyl-2-propen-1-ol (CH2C(CH3)CH2OH) (2) and 2-buten-1-ol (CH3CHCHCH2OH) (3) in water. The most reactive substrate, (1), with a terminal double bond, is hydrogenated at 313 K and 0.1 MPa of H2 pressure giving 92% of 2-methyl-propanol after
Acta Crystallographica Section C Crystal Structure Communications, 2006
The title compound, [Pd2(C12H10O3P)2Cl2(C12H11O3P)2], consists of a dinuclear mu-chloro-bridged p... more The title compound, [Pd2(C12H10O3P)2Cl2(C12H11O3P)2], consists of a dinuclear mu-chloro-bridged palladium unit with two diphenoxyphosphinite groups per Pd atom, linked together by a hydrogen bond. The asymmetric unit contains one half of the molecule, with the other half generated by an inversion centre. The geometry around the P atoms may be described as distorted tetrahedral. Adjacent molecules of the complex are linked by weak C-H...O and C-H...Cl hydrogen bonds. The structure is additionally stabilized by pi-pi stacking interactions between the aryl rings. These interactions form a herring-bone pattern in the crystal structure.
New Journal of Chemistry, 2008
ABSTRACT Cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) in the form of gel-t... more ABSTRACT Cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) in the form of gel-type beads was used to encapsulate Pd(0)nanoparticles 4–15 nm in diameter and applied as a new, reusable catalyst for the Suzuki–Miyaura cross-coupling reaction of 2- and 4-bromotoluene with phenylboronic acid. It was found that the precatalyst preparation methodology strongly influenced its catalytic activity. The best results (100% yield of the product) were obtained when GMA-CHDA was first treated with hydrazine (reducing agent for Pd(II)) and next with PdCl2 solution. The new catalyst acts heterogeneously, and the post-reaction solution after catalyst separation is not catalytically active, suggesting that there is no leaching.
Journal of Organometallic Chemistry, 1999
The novel rhodium complexes with the bidentate PO ligand (PO = OC 6 H 4 PPh 2 − ) of the form Rh(... more The novel rhodium complexes with the bidentate PO ligand (PO = OC 6 H 4 PPh 2 − ) of the form Rh(PO)(CO)L (L a =POH= HOC 6 H 4 PPh 2 (1), PPh 3 (2), P(NC 4 H 4 ) 3 (4), PPh 2 (NC 4 H 4 ) (6)) and Rh(PO)L 2 (L b = P(OPh) 3 (3), P(NC 4 H 4 ) 3 (5)) were obtained by ligand exchange in Rh(b-diketone)(CO) 2 , Rh(b-diketone)(CO)L and Rh(b-diketone)L 2 complexes. All complexes of the Rh(PO)(CO)L a type exist in solution as isomers with both phosphorus atoms in the trans position as was shown by 31 P{ 1 H}-NMR. The trans influence of the phosphorus atom of a bidentate PO ligand is stronger than that of oxygen atom, which is manifested by the differences of Rh-P bonds in (2) (2.283(1) and 2.327(1) Å ) and of Rh -P (phosphite) bonds in (3) (2.233(2) and 2.139(2) Å ). The complexes (1) and (2) used alone or with an excess of free phosphine (POH, PPh 3 , P(NC 4 H 4 ) 3 ) are not active in hexen-1-e hydroformylation at 1 MPa CO/H 2 =1 and at 353 K. The lack of catalytic activity is explained by the extremely high stability of the chelate (PO) ring which does not allow the formation of the active form of the catalyst. In contrast, the complex (3) used alone as the catalyst precursor produces 54 and 72.9% of aldehydes when used with a six-fold excess of P(OPh) 3 . Complex (1) modified with P(OPh) 3 catalyses hexen-1-e hydroformylation with a 73.6 -84.6% yield of aldehydes. Under hydroformylation reaction conditions, the PO ligand is removed from the coordination sphere of (1) and complexes of the form HRh(CO){P(OPh) 3 } 3 and HRh{P(OPh) 3 } 4 are formed.
Journal of Organometallic Chemistry, 2001
The substitution of CO ligand in rhodium(I) β-ketoiminato complexes Rh(R1{O,N}R2)(CO)2 ({O,N}=R1... more The substitution of CO ligand in rhodium(I) β-ketoiminato complexes Rh(R1{O,N}R2)(CO)2 ({O,N}=R1C(O)CHC(NH)R2; R1, R2=CF3, Me, CMe3 in several combinations) by phosphorus ligands PZ3 (PZ3=PCy3, PPh3, P(OPh)3, P(NC4H4)3) leads to Rh(R1{O,N}R2)(CO)(PZ3) complexes characterised by 31P{1H}-NMR and X-ray methods. The stronger σ-donor PZ3 ligands (PZ3=PCy3, PPh3) substitute almost exclusively the CO group trans to N, forming P-trans-to-N isomers. The complexes Rh(CF3{O,N}Me)(CO)(PCy3) (II), Rh(CF3{O,N}CMe3)(CO)(PCy3) (III), Rh(CF3{O,N}Me)(CO)(PPh3) (IV) and Rh(CF3{O,N}CMe)(CO)(PPh3) (V) are of a square-planar geometry with a slight tetrahedral distortion around the rhodium atom in II, III and V. The Rh-P(PCy3) bonds are slightly longer than the Rh-P(PPh3) bonds. The reaction of stoichiometric amounts of the less basic P(OPh)3 or P(NC4H4)3 ligands leads to the formation of both isomers of the Rh(R1{O,N}R2)(CO)(P(OPh)3) or Rh(R1{O,N}R2)(CO)(P(NC4H4)3) complex in comparable yields. The Rh-P(P(OPh)3) distance (2.195(2) Å) in the isomer of Rh(CF3{O,N}CMe3)(CO)(P(OPh)3) with P(OPh)3 coordinated trans to N (VI) is ca. 0.04 Å longer than in the isomer of that complex with P(OPh)3 coordinated trans to O (VII). The CO substitution in Rh(R1{O,N}R2)(CO)2 by PZ3 ligands (PPh3, PCy3, P(OPh)3) causes the shortening of the Rh-C(CO) bond by ca. 0.04 Å compared to Rh(CF3{O,N}Me)(CO)2 (I). The more π-acceptor P(OPh)3 ligands form bis-phosphito complexes; Rh(CF3{O,N}CMe3){P(OPh)3}2 (VIII) exhibits inequivalence of the two P(OPh)3 ligands in solution (31P-NMR) as well as in solid form (X-ray).
Journal of Molecular Catalysis A: Chemical, 2004
Journal of Molecular Catalysis …, 1996
... Journal of Molecular Catalysis A: Chemical 110 (1996) 135139 JOURNAL OF MOLECULAR CATALYSIS 1... more ... Journal of Molecular Catalysis A: Chemical 110 (1996) 135139 JOURNAL OF MOLECULAR CATALYSIS 10 A: CHEMICAL New bimetallic rhodiumzirconium catalysts for homogeneous olefin hydroformylation Anna M. Trzeciak a ... [9] AM Trzeciak, M. Jon and JJ Ziolkowski, React. ...
Applied Catalysis A: General, 2010
Two palladium catalyst precursors were prepared by immobilizing PdCl2 and Pd(OAc)2 on cyclohexyld... more Two palladium catalyst precursors were prepared by immobilizing PdCl2 and Pd(OAc)2 on cyclohexyldiamine-modified glycidyl methacrylate polymer (GMA-CHDA) and used in the Suzuki–Miyaura reaction (80°C, 2h) without any pre-treatment. Using the TEM, SEM, EDS, and XPS methods, we were able to characterize the Pd(0) nanoparticles formed in situ during the catalytic process. The catalyst obtained from Pd(OAc)2 (P2) contained Pd(0) nanoparticles
Catalysis Letters, 2006
Efficient cross-coupling and carbonylative coupling of terminal alkynes with aryl iodides catalyz... more Efficient cross-coupling and carbonylative coupling of terminal alkynes with aryl iodides catalyzed by PdCl 2 (P(OPh) 3 ) 2 in the presence of NEt 3 in toluene and in ionic liquids is described. In imidazolium ionic liquids, [bmim]PF 6 or [mokt]PF 6 (bmim = 1butyl-3-methyl imidazolium cation, mokt=1-methyl-3-octyl imidazolium cation) catalyst was recycled and used in four concecutive catalytic cycles with high activity. In the absence of aryl iodide the same catalytic system catalyzed head-to-tail dimerization of phenylacetylene to the 1,3-diphenyl enyne, trans-PhC CAC(Ph)@CH 2 ; with a yield of 85%.