(1-(Dimethylamino)-2-(diphenylphosphino)ethane)(η<sup>3</sup>-1-arylallyl)palladium Tetrafluoroborates. Preparation, Isomeric Equilibria, and Correlations of NMR Chemical Shifts with Hammett Substituent Constants

Malet, R.; Moreno‐Mañas, Marcial; Parella, Teodor; Pleixats, Roser

doi:10.1021/jo9514331

Cited by 26 publications

(15 citation statements)

References 46 publications

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“…The volatile compounds were then removed from the solution, and (P ʝ N)Pt(Me)Cl (2) remained as a colorless powder in a quantitative yield. 1 [5] with P ʝ N: A solution of [2-(diphenylphosphanyl)ethyl]dimethylamine (P ʝ N) [20] (282 mg, 1.09 mmol) in 10 mL of CH 2 Cl 2 was added slowly to a solution of (nbd)Pt(Me)Cl (365 mg, 1.08 mmol) in 40 mL of CH 2 Cl 2 . After the mixture was stirred for 1 h, the colorless product was filtered and washed with benzene (3 ϫ 5 mL) and pentane (3 ϫ 5 mL).…”

Section: Methodsmentioning

confidence: 99%

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C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Stöhr

Sturmayr

Kickelbick

et al. 2002

Eur. J. Inorg. Chem.

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The complex [(κ2‐P,N)‐Ph2PCH2CH2NMe2]PtMe2 reacts with chlorinated hydrocarbons such as CCl4, CHCl3, CH2Cl2, and CH3Cl by oxidative addition of the C−Cl bond. In the reaction with CCl4, the complexes [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)Cl, [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)3Cl, and [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(CCl=CH2)Cl are obtained. The analogous P,P‐chelated complex [(κ2‐P,P)‐Ph2CH2CH2PPh2]PtMe2 does not react under the same conditions. Reaction of [(κ2‐P,N)‐Ph2PCH2CH2NMe2]PtMe2 with ClSiMe2Ph results in the formation of Ph2Me4Si2 along with [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)Cl and [(κ2‐P,N)‐Ph2PCH2CH2NMe2]Pt(Me)3Cl. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Methodsmentioning

confidence: 99%

“…The C(9) atom of the ethylene bridge is also disordered. The PtϪC distances of the equatorial methyl substituents [PtϪC(20): Molecular structure of [(κ 2 -P,N)-Ph 2 PCH 2 CH 2 NMe 2 ]-Pt(Me)3 Cl(4)…”

mentioning

confidence: 99%

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Stöhr

Sturmayr

Kickelbick

et al. 2002

Eur. J. Inorg. Chem.

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“…The trend of tuning the endo/exo ratio has been reported mainly for symmetrically disubstituted allyl complexes, while very few papers have mentioned cis/trans control. [17,23,43] All the complexes studied in this paper provide evidence of the influence of the steric bulkiness of the nitrogen substituent on the diastereomeric ratio. Yellow crystals of compound 6 were grown from dichloromethane/pentane.…”

mentioning

confidence: 70%

“…[14,19,35] You et al have observed that, for a complex containing the 2-(phenylthio)-1-(4-tert-butyloxazolinyl)ferrocene ligand, an inversion of the configuration of the oxazoline ring asymmetric carbon slightly affects the endo/exo ratio (3.1:1 vs. 2.1:1), whereas introducing two benzylic groups at the 4-position of the oxazoline ring strongly displaces the equilibrium in favour of the endo diastereomer. [36] The preferential nucleophilic attack at one specific allyl carbon atom is another way to achieve high enantioselectiv- Table 1. 13 C NMR spectroscopic data for allylic carbon atoms in complexes 1 and 2 [14,23,28,37] For complexes 1 and 2, ∆δ lies between 35.7 and 27.2 ppm depending on the isomer (see Table 1). Such a high ∆δ is usual for N,P ligands, given the very different trans influence of the phosphorus and nitrogen atoms, [26] and reveals a higher electrophilicity for the C-1 atom (trans-P) than for the C-3 atom (cis-P; see Scheme 2).…”

Section: Nmr Spectroscopic Studies On Allylic Compounds 1 Andmentioning

confidence: 99%

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Allylpalladium(II) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis‐[Pd(η³‐CH₂CHCHPh){Ph₂PCH₂CHPhNH(2,6‐C₆H₃iPr₂)}][PF₆]

et al. 2004

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A new β-aminophosphane L 2 [Ph 2 PCH 2 CH(Ph)NH(2,6-C 6 H 3 iPr 2 )], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η 3 -allyl)palladium complexes of general formula [Pd(η 3 -C 3 H 4 R){η 2 -Ph 2 PCH 2 CH-(Ph)NHAr}][PF 6 ] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6-C 6 H 3 iPr 2 ) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6-C 6 H 3 iPr 2 ) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η 3 -C 3 H 4 R){Ph 2 PCH 2 CH(Ph)NHAr}][PF 6 ] (3−6, R = Me or Ph) only cis/trans-P and endo/exo isomers with syn-oriented allyl substituents have been observed in solution. The diastereom-

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Chiral Boron‐Bridged Bisoxazoline (Borabox) Ligands: Structures and Reactivities of Pd and Cu Complexes

Köhler

Mazet

Toussaint

et al. 2008

Chemistry A European J

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Anionic boron-bridged bisoxazolines (borabox ligands) have been synthesized and characterized in their protonated forms. The ligands are tuneable over a wide range, allowing either alkyl or aryl substituents at the oxazoline rings and the central bridging boron atom. The structural parameters of this new ligand type have been investigated by X-ray analyses of palladium and copper complexes. Electronic properties have been studied by (13)C NMR spectroscopy and by DFT calculations on palladium allyl complexes and compared to those of analogous bisoxazoline (box) complexes. Borabox complexes are more electron-rich at the metal center than their neutral box congeners, and as a consequence of the longer bonds between the bridging atom and the oxazoline rings, their bite angles are larger. Palladium(II) complexes bearing an unsubstituted allyl ligand and homoleptic copper(II) complexes each possess an almost flat chelate ring. NMR analysis of a (1,3-diphenylallyl)(borabox)palladium complex showed a 92:8 mixture of (syn,syn) and (anti,syn) allyl isomers, in contrast with a previously reported box analogue that existed exclusively in the (syn,syn) form. Comparison of the corresponding crystal structures revealed that the distance between the bisoxazoline and the allyl ligand in the borabox complex is shorter. In the copper-catalyzed allylic oxidation of cyclohexene and cyclopentene with tert-butyl perbenzoate, borabox ligands gave results similar-and in some cases superior-to those obtained with analogous box ligands.

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(1-(Dimethylamino)-2-(diphenylphosphino)ethane)(η³-1-arylallyl)palladium Tetrafluoroborates. Preparation, Isomeric Equilibria, and Correlations of NMR Chemical Shifts with Hammett Substituent Constants

Cited by 26 publications

References 46 publications

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Allylpalladium(II) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis‐[Pd(η³‐CH₂CHCHPh){Ph₂PCH₂CHPhNH(2,6‐C₆H₃iPr₂)}][PF₆]

Chiral Boron‐Bridged Bisoxazoline (Borabox) Ligands: Structures and Reactivities of Pd and Cu Complexes

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(1-(Dimethylamino)-2-(diphenylphosphino)ethane)(η3-1-arylallyl)palladium Tetrafluoroborates. Preparation, Isomeric Equilibria, and Correlations of NMR Chemical Shifts with Hammett Substituent Constants

Cited by 26 publications

References 46 publications

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

C−Cl and Si−Cl Activation byP,N-Chelated PtII Complexes

Allylpalladium(II) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis‐[Pd(η3‐CH2CHCHPh){Ph2PCH2CHPhNH(2,6‐C6H3iPr2)}][PF6]

Chiral Boron‐Bridged Bisoxazoline (Borabox) Ligands: Structures and Reactivities of Pd and Cu Complexes

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(1-(Dimethylamino)-2-(diphenylphosphino)ethane)(η³-1-arylallyl)palladium Tetrafluoroborates. Preparation, Isomeric Equilibria, and Correlations of NMR Chemical Shifts with Hammett Substituent Constants

Allylpalladium(II) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis‐[Pd(η³‐CH₂CHCHPh){Ph₂PCH₂CHPhNH(2,6‐C₆H₃iPr₂)}][PF₆]