Synthesis, characterization and reactivity of ionic palladium(II) complexes containing bidentate nitrogen ligands in a unidentate coordination mode,

Groen, J.H.; Jong, B.J. de; Ernsting, Jan Meine; Leeuwen, Piet W. N. M. van; Vrieze, K.; Smeets, Wilberth J. J.; Spek, Anthony L.

doi:10.1016/s0022-328x(98)00596-8

Cited by 28 publications

(8 citation statements)

References 40 publications

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“…In the case of the Pd complexes, for this mechanism to be operative the cleavage of one PdÀN bond is required, which is likely to occur as evidenced by NEB calculations and thanks to the lability of the PdÀN bond. [24,43,44] A NOESY experiment performed at room temperature on complex 1 BIANa reveals for each isomer an exchange peak between H 3 and H 10 , thus supporting the hypothesized mechanism ( Figure S17).…”

Section: Synthesis and Characterization Of Ligands And Their Pd II Cosupporting

confidence: 59%

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

et al. 2014

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The catalytic CO/styrene and ethylene/methyl acrylate copolymerizations are compared for the first time by applying the same precatalysts. With this aim, PdII neutral, [Pd(CH3)Cl(N–N)], and monocationic, [Pd(CH3)(L)(N–N)][PF6] (L=CH3CN, DMSO), complexes with 1-naphthyl- and 2-naphthyl-substitued α-diimines with both an acenaphthene and a diazabutadiene skeleton as chelating nitrogen-donor ligands (N–N) have been studied. In the case of the complexes with the 1-naphthyl-substituted ligands, syn and anti isomers are found both in solid state and in solution. All the monocationic complexes generate active catalysts for the CO/styrene copolymerization leading to atactic or isotactic/atactic stereoblock copolymers depending on the ligand bonded to palladium. Instead, in the case of the ethylene/methyl acrylate copolymerization only the complexes with the 1-naphthyl-substituted ligands generate catalysts for this reaction

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Section: Synthesis and Characterization Of Ligands And Their Pd II Cosupporting

confidence: 59%

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

et al. 2014

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“…The suitable catalytic properties of bis(arylimino)acenaphthene complexes arise from the presence of two exocyclic chelating imine groups coupled with rigidity of the acenaphthene backbone, thus preventing rotation about the imine C−C bond. To analyze the stereochemical features of the BIAN moiety in 9 , its geometric parameters can be compared with those of the free ligand 12 and the Pd derivatives containing Ar-BIAN ligands. ,− First of all, the acenaphthene unit in 9 exhibits a bonding geometry coherent with a classical resonance picture giving rise to higher bond order for the C(4)−C(5), C(6)−C(7), C(9)−C(10), and C(11)−C(12) bonds; a similar trend appears in free bis( p -tolylimino)acenaphthene 12 and the Pd complexes with bis( o , o ‘-diisopropylphenylimino)-, , bis( p -tolylimino)-, and bis( p -anisylimino)acenaphthene . Therefore, analogously to the other BIAN complexes, in 9 the naphthalene backbone shows no significant conjugation with the bisimine moiety.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of N-Arylpyrroles, Hetero-Diels−Alder Adducts, and Allylic Amines by Reaction of Unfunctionalized Dienes with Nitroarenes and Carbon Monoxide, Catalyzed by Ru(CO)₃(Ar-BIAN)

Ragaini¹,

Cenini²,

Borsani³

et al. 2001

Organometallics

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The reaction between an unfunctionalized conjugated diene and a nitroarene under CO pressure, catalyzed by Ru 3 (CO) 12 /Ar-BIAN (Ar-BIAN ) bis(arylimino)acenaphthene), affords the corresponding allylic amine (1), the hetero-Diels-Alder adduct (oxazine) (2), and the N-arylpyrrole (3) in different ratios depending on the experimental conditions. The synthesis of the allylic amine involves an intermolecular catalytic C-H functionalization by a transition metal complex. Compounds 1 and 2 are primary products of the reaction, whereas 3 derives from a following reaction of 2. By running the reaction at 120 °C, the decomposition of 2 to 3 is completely suppressed, allowing for the isolation of 2 in good yields. On the contrary, at 200 °C 2 is completely transformed into 3 during the reaction. The selectivity in allylic amine is somewhat sensitive to the experimental conditions and always ranges between 15 and 25%. Electron-withdrawing substituents on the nitroarene give better results, but electrondonating ones slow the reaction and give lower selectivities. Steric hindrance on the nitroarene strongly retards the reaction, but use of 2-methylnitrobenzene allowed for the isolation and X-ray structural characterization of a resting state of the catalytic system, Ru[N(o-CH 3 C 6 H 4 )C(O)N(o-CH 3 C 6 H 4 )C(O)](CO) 2 (Ph-BIAN) (9).

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“…The insertion of CO into the Pd−C bond, resulting in the formation of acylpalladium derivatives, constitutes a key step in the palladium-catalyzed carbonylation of organic substrates in laboratory synthesis and also in industrial processes. − These CO insertions are also relevant in the palladium-catalyzed copolymerization of CO and unsaturated organic substrates. − This is the reason for the extensive study of insertion reactions. ,− However, most studies of insertion reactions of CO into Pd−C bonds have been devoted to alkyl, mainly methyl, derivatives. ,,− Only mononuclear phenyl- or alkyl-substituted phenyl 46,51-56 and dinuclear 1,4-phenylene and 4,4‘-biphenyl palladium complexes have been carbonylated. The rates of reaction of a variety of trans -[Pd(Ar)X(PPh 3 ) 2 ] (Ar = C 6 H 4 R-4, R = H, NO 2 , Me, CN, CF 3 , OMe; X = Cl, Br, I) complexes with CO have been studied, but the resulting complexes have not been isolated .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles

et al. 2001

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The reaction of 2-ROC6H4I with [Pd2(dba)3]·dba (“Pd(dba)2”; dba = dibenzylideneacetone) in the presence of the appropriate ligand results in the formation of the arylpalladium complexes trans-[Pd(C6H4OR-2)I(PPh3)2] (R = H (1a), C(O)Me (1b), C(O)CHCH2 (1c)) and [Pd(C6H4OR-2)I(bpy)] (bpy = 2,2‘-bipyridine; R = H (2a), C(O)Me (2b)). Complexes 1b and 1c react with bpy in the presence of Tl(OTf) (OTf = OSO2CF3) to give the cationic species [Pd(C6H4OR-2)(bpy)(PPh3)]OTf (R = C(O)Me (3b), C(O)CHCH2 (3c)). Complex 1a reacts with carbon monoxide, yielding the insertion complex trans-[Pd{C(O)C6H4OH-2}I(PPh3)2] (4a). Complexes 2a and 2b can also be carbonylated to give [Pd{C(O)C6H4OR-2}I(bpy)] (R = H (5a), C(O)Me (5b)). Complex 4a reacts with bpy and Tl(OTf), giving [Pd{C(O)C6H4OH-2}(bpy)(PPh3)]OTf (6a). The reaction of 2-ROC6H4I with Pd(dba)2 and isonitriles R‘NC gives rise to the complexes trans-[Pd{C(NR‘)C6H4OR-2}I(CNR‘)2] (R = H, R‘ = Xy = 2,6-dimethylphenyl) (7a), R‘ = t Bu (7a*); R = C(O)Me, R‘ = Xy (7b), R‘ = t Bu (7b*)). Complexes 7a and 7b* can also be prepared by ligand displacement from 2a and 2b and XyNC and t BuNC, respectively. Complexes 2a and 2b react with R‘NC (1:1) to give [Pd{C(NR‘)C6H4OR-2}I(bpy)] (R = H, R‘ = Xy (8a), R‘ = t Bu (8 a *); R = C(O)Me, R‘ = Xy (8b)). Complex 7a reacts with bpy in the presence of Tl(OTf), yielding [Pd{C(NR‘)C6H4OH-2}(CNR‘)(bpy)]OTf (9a). Reaction of 5a with R‘NC gives trans-[Pd{C(O)C6H4OH-2}I(CNR‘)2] (R‘ = Xy (10a), t Bu (10 a *)), which, in turn, react with further R‘NC in the presence of Tl(OTf) to give [Pd{C(O)C6H4OH-2}(CNR‘)3]OTf (R‘ = Xy (11a), t Bu (11 a *)). Finally, the reaction of 7a with Pd(OAc)2 results in the tetrameric [Pd{κ 2(C,O)- μ 2(O)-C(NXy)C6H4O-2}(CNXy)]4 (12) and trans-[PdI2(CNXy)2]. Most of the reported aroyl (4−6, 10, 11) and iminoaroyl (7−9, 12) derivatives are new types of palladium complexes. The crystal structures of complexes 5a, 7a, 7b, 8b, 9a, and 12 have been determined by X-ray diffraction methods. The following scale of trans influence has been established: bpy < I < C(NXy)C6H4OC(O)Me-2 ≈ C(O)C6H4OH-2 < C(NXy)C6H4OH-2.

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Synthesis, characterization and reactivity of ionic palladium(II) complexes containing bidentate nitrogen ligands in a unidentate coordination mode,

Cited by 28 publications

References 40 publications

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Synthesis of N-Arylpyrroles, Hetero-Diels−Alder Adducts, and Allylic Amines by Reaction of Unfunctionalized Dienes with Nitroarenes and Carbon Monoxide, Catalyzed by Ru(CO)₃(Ar-BIAN)

Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles

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Synthesis, characterization and reactivity of ionic palladium(II) complexes containing bidentate nitrogen ligands in a unidentate coordination mode,

Cited by 28 publications

References 40 publications

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Analogies and Differences in Palladium‐Catalyzed CO/Styrene and Ethylene/Methyl Acrylate Copolymerization Reactions

Synthesis of N-Arylpyrroles, Hetero-Diels−Alder Adducts, and Allylic Amines by Reaction of Unfunctionalized Dienes with Nitroarenes and Carbon Monoxide, Catalyzed by Ru(CO)3(Ar-BIAN)

Synthesis of Ortho-Palladated Phenol Derivatives. Study of Their Reactivity with Carbon Monoxide and Isonitriles

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Synthesis of N-Arylpyrroles, Hetero-Diels−Alder Adducts, and Allylic Amines by Reaction of Unfunctionalized Dienes with Nitroarenes and Carbon Monoxide, Catalyzed by Ru(CO)₃(Ar-BIAN)