Preparation of binuclear complexes using 2-(diphenylphosphino)pyridine as a bridging ligand. Synthesis of some ruthenium complexes and their interaction with palladium complexes

Maisonnet, Andre.; Farr, James P.; Olmstead, Marilyn M.; Hunt, Catherine T.; Balch, Alan L.

doi:10.1021/ic00141a020

Cited by 98 publications

(21 citation statements)

References 2 publications

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“…Finally, the Pd-N bond lengths in 7 are within -0.02 A of those in 6c and the other PPh2py systems mentioned above, Pd-Mo (1 l), Pd-Rh (15), and Pd-Ru (21), but the Pd-P bond in 7 is the longest observed (by up to 0.05 A), perhaps reflecting a somewhat more electronegative effect for the pyridyl (vs. phenyl) substituent.…”

Section: Results and Discussion The Pdx2(pph3-npyn)2 Cornplexessupporting

confidence: 52%

“…The torsion angles (Table 4) show that the five-membered rings are very nonplanar, but the relative orientation of the two bridging ligands still leaves a pans arrangement of P and N at each metal. This is found also in PdCl(PPh,py),-RhCl(CO), which is four-coordinate at the Pd and six-coordinate at the Rh (15), but in PdCl(PPh,py),RuCl(CO),, also a four-and six-coordinate system (21), and in PdC1-(PPh2py)2(p-CO)M~C1(CO), (1 1) Deviations (A, A) from mean planes of the ligand atoms at palladium centres for Pd,I,(PPh,py),, 6c, and PdzClz(Ppy,),(pDMAD), 7 , and at the (=C-C(0)OMe) fragments of 7" Atom Deviation Atom Deviation…”

Section: Results and Discussion The Pdx2(pph3-npyn)2 Cornplexesmentioning

confidence: 68%

“…CHCI, (20), PPh2py (21), and Ppy, (22) were repared by the literature proce-P dures. 31P{'H} (121.4 MHz) and 'c{'H} (75.4 MHz) NMR spectra were recorded on a Varian XL-300 instrument.…”

Section: Methodsmentioning

confidence: 99%

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Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

Xie¹,

Lee²,

Yang³

et al. 1992

Can. J. Chem.

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. Can. J. Chcm. 70, 751 (1992). phosphine]palladium(II) complexes are prepared by metathesis of cis-PdC1,(PPh3-,,py,,), species (n = 1-3) using the appropriate sodium halide; py = 2-pyridyl. NMR spectroscopy, particularly ' 3~{ 1~} , is used to distinguish cis and trans isomers. The dinuclear complexes Pd2X2(k-PPh3-,,py,,),, X = halide, are synthesized via a conproportionation reaction using PdX, (PPh,-,,py,,), and Pd,(dba),; dba = dibenzylideneacetone. Both Pd211(k-PPh,py), and a dimethylacetylenedicarboxylate A-frame complex Pd,Cl2(k-Ppy3),(~-MeO?_C . C=C . C02Me) are characterized crystallographically as head-to-tail isomer:. ' The former crystallizes in the monoclinic space group C 2 / c with a = 30.992(3), b = 18.764(1), c = 13.100(1) A, P = 100.676(5)", and Z = 8; the dcta were refined to R = 0.035 for 5874 reflections withal 2 3u(I). The A-frame compound is triclinic of space group PI with a = 13.545(2), b = 15.064(2), c = 11.991(2) A, a = 1 l1.56(1), P = 95.36(1), y = 97.63(1)", and Z = 2; R = 0.033 from 7128 reflections with I ? 3u(I). The Pd,X2(k-PPhpy,)2 complexes exist as a mixture of diastereomers because of chirality induced at the phosphorus atoms. The Pd,X,(k-Ppy,)? complexes in water generate the [ P~~( H~O )~(~-P P~~) $ + dication, which is isolated as various salts. The mononuclear complexes in water generate aquo and hydroxo species.Key words: dimethylacetylenedicarboxylate adducts, palladium complexes (dinuclear), pyridylphosphines. que l'on a isole sous la forme du plusieurs sels. Dans l'eau, les complexes mononuclCaires fournissent des espkces aquo et hydroxo.Mots cle's : adduits de 1'acCtylknedicarboxylate de dimCthyle, complexes dinucleaires du palladium, pyridylphosphines.[Traduit par la rtdaction]

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Section: Results and Discussion The Pdx2(pph3-npyn)2 Cornplexessupporting

confidence: 52%

Section: Results and Discussion The Pdx2(pph3-npyn)2 Cornplexesmentioning

confidence: 68%

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Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

Xie¹,

Lee²,

Yang³

et al. 1992

Can. J. Chem.

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“…5 In many instances binuclear complexes in which the ligand bridges the metal-metal bond are preferred. [31][32][33][34][35][36][37][38][39][40]…”

Section: Introductionmentioning

confidence: 99%

The synthesis of, and characterization of the dynamic processes occurring in Pd(ii) chelate complexes of 2-pyridyldiphenylphosphine

et al. 2010

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Pd(II) complexes in which 2-pyridyldiphenylphosphine (Ph(2)Ppy) chelates the Pd(II) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans-[Pd(kappa(1)-Ph(2)Ppy)(2)Cl(2)] is transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]X by addition of AgX or TlX, (X = BF(4)(-), CF(3)SO(3)(-) or MeSO(3)(-)). [Pd(kappa(1)-Ph(2)Ppy)(2)(p-benzoquinone)] can be transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)(MeSO(3))][MeSO(3)] by the addition of two equivalents of MeSO(3)H. Addition of further MeSO(3)H affords [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)PpyH)(MeSO(3))][MeSO(3)](2). Addition of two equivalents of CF(3)SO(3)H, MeSO(3)H or CF(3)CO(2)H and two equivalents of Ph(2)Ppy to [Pd(OAc)(2)] in CH(2)Cl(2) or CH(2)Cl(2)-MeOH affords [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)X]X, (X = CF(3)SO(3)(-), MeSO(3)(-) or CF(3)CO(2)(-)), however addition of two equivalents of HBF(4).Et(2)O affords a different complex, tentatively formulated as [Pd(kappa(2)-Ph(2)Ppy)(2)]X(2). Addition of excess acid results in the clean formation of [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)PpyH)(X)]X(2). In methanol, addition of MeSO(3)H and three equivalents of Ph(2)Ppy to [Pd(OAc)(2)] affords [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)(2)][MeSO(3)](2) as the principal Pd-phosphine complex. The fluxional processes occuring in these complexes and in [Pd (kappa(1)-Ph(2)Ppy)(3)Cl]X, (X = Cl, OTf) and the potential for hemilability of the Ph(2)Ppy ligand has been investigated by variable-temperature NMR. The activation entropy and enthalpy for the regiospecific fluxional processes occuring in [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)(2)][MeSO(3)](2) have been determined and are in the range -10 to -30 J mol(-1) K(-1) and ca. 30 kJ mol(-1) respectively, consistent with associative pathways being followed. The observed regioselectivities of the exchanges are attributed to the constraints imposed by microscopic reversibility and the small bite angle of the Ph(2)Ppy ligand. X-Ray crystal structure determinations of trans-[Pd(kappa(1)-Ph(2)Ppy)(2)Cl(2)], [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl][BF(4)], [Pd(kappa(1)-Ph(2)Ppy)(2)(p-benzoquinone)], trans-[Pd(kappa(1)-Ph(2)PpyH)(2)Cl(2)][MeSO(3)](2), and [Pd(kappa(1)-Ph(2)Ppy)(3)Cl](Cl) are reported. In [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl][BF(4)] a donor-acceptor interaction is seen between the pyridyl-N of the monodentate Ph(2)Ppy ligand and the phosphorus of the chelating Ph(2)Ppy resulting in a trigonal bipyramidal geometry at this phosphorus.

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“…Ir4 (CO) 12 was obtained in quantitative yield by the reaction of IrC13.3H20 or (NH4)zIrC16 with formic acid (HCOOH).9 All substitution reactions i n Ir4(CO) 12 were carried out under a carbon monoxide (COj atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Iridium carbonyl clusters with pyridylphosphines: [Ir₄(CO)₉(PPh_xpyl_3−x)₃]

Wajda-Hermanowicz¹,

Koralewicz²,

Pruchnik³

1990

Applied Organom Chemis

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[Ir4(CO)9(PR3)3] type complexes were obtained in the reaction between Ir4(CO)12 and the 2-pyridylphosphines: diphenyl(2-pyridy1)phosphine (PPh2pyl), phenylbis(2-pyridy1)phosphine (PPhpy12), tris-(2-pyridyl)phosphine (Ppy13) (pyl = 2-pyridyl) in methanol in basic medium, in the presence of carbon monoxide. The reaction conditions were determined and the products were spectroscopically characterized.

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Preparation of binuclear complexes using 2-(diphenylphosphino)pyridine as a bridging ligand. Synthesis of some ruthenium complexes and their interaction with palladium complexes

Cited by 98 publications

References 2 publications

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

The synthesis of, and characterization of the dynamic processes occurring in Pd(ii) chelate complexes of 2-pyridyldiphenylphosphine

Iridium carbonyl clusters with pyridylphosphines: [Ir₄(CO)₉(PPh_xpyl_3−x)₃]

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Preparation of binuclear complexes using 2-(diphenylphosphino)pyridine as a bridging ligand. Synthesis of some ruthenium complexes and their interaction with palladium complexes

Cited by 98 publications

References 2 publications

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd2I2(µ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(µ-Ppy3)2(µ-MeO2C•C=C•CO2Me); py = 2-pyridyl

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd2I2(µ-PPh2py)2 and a dimethylacetylenedicarboxylate A-frame complex Pd2Cl2(µ-Ppy3)2(µ-MeO2C•C=C•CO2Me); py = 2-pyridyl

The synthesis of, and characterization of the dynamic processes occurring in Pd(ii) chelate complexes of 2-pyridyldiphenylphosphine

Iridium carbonyl clusters with pyridylphosphines: [Ir4(CO)9(PPhxpyl3−x)3]

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Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

Mono- and dinuclear palladium complexes containing 2-pyridylphosphine ligands, including X-ray characterization of Pd₂I₂(µ-PPh₂py)₂ and a dimethylacetylenedicarboxylate A-frame complex Pd₂Cl₂(µ-Ppy₃)₂(µ-MeO₂C•C=C•CO₂Me); py = 2-pyridyl

Iridium carbonyl clusters with pyridylphosphines: [Ir₄(CO)₉(PPh_xpyl_3−x)₃]