Cationic palladium(II)-allyl-complexes containing 2-pyridyldiphenylphosphine: X-ray crystal structure of the binuclear complex [Pd(η3-2-Me-allyl)(μ-Ph2PPy)]2(BF4)2. Detection of an intramolecular C(allyl)–H⋯phenyl ring π-interaction

Scrivanti, Alberto; Benetollo, Franco; Venzo, Alfonso; Bertoldini, Matteo; Beghetto, Valentina; Matteoli, Ugo

doi:10.1016/j.jorganchem.2007.04.021

Cited by 13 publications

(11 citation statements)

References 27 publications

(28 reference statements)

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“…In the 13 C{ 1 H} NMR spectrum the two terminal carbon atoms of the allyl moiety are chemically but not magnetically equivalent and give rise to an AA 0 X resonance centered at d 80.6, while the central carbon resonance is a triplet at d 140.0 as found for the parent complex 3 [15]. These data show that also the allyl carbon atoms of 3a are significantly deshielded upon protonation.…”

Section: Protonation Of Complexmentioning

confidence: 73%

“…Commercial Ph 2 PPy (Aldrich) was recrystallized from methanol. [Pd(g 3 -2-CH 3 -C 3 H 4 )Cl] 2 [31], [PdCl(g 3 -2-CH 3 -C 3 H 4 )(Ph 2 PPy)] [9,14], [Pd 2 (g 3 -2-CH 3 -C 3 H 4 ) 2 (l-Ph 2 PPy) 2 ](BF 4 ) 2 [15] and [Pd(g 3 -2-CH 3 -C 3 H 4 ) (Ph 2 PPy) 2 ](BF 4 ) [15] were prepared according to literature methods. …”

Section: Methodsmentioning

confidence: 99%

“…The 31 P NMR spectrum of 1 consists of a singlet at d 26.0 [15] which moves downfield to d 26.8 upon protonation; it is worth noting that the Dd (+0.8, at 253 K) is much smaller and opposite in sign to that observed in the protonation of the free ligand (Dd = À3.0).…”

Section: Protonation Of Complexmentioning

confidence: 95%

“…The complexes 1 [10,14], 2 [15] and 3 [15] were prepared according to the literature as outlined in Scheme 2. The hitherto unreported Pd(0)-olefin complex 4 was obtained in good yield by treating complex 3 with three equivalents of diethylamine in the presence of fumaronitrile according to a well-know method for the synthesis of zerovalent palladium olefin complexes [16,17].…”

Section: Synthesis and Characterization Of The Palladium Complexesmentioning

confidence: 99%

“…For instance, it is well-know that the dynamic behavior of Pd-allyl complexes is strongly affected by the electronic and steric properties of the ancillary ligands [12,13]. In this connection, it is worth of note that the reports dealing with palladium allyl complexes containing Ph 2 PPy are rare [6a, 9,14,15]. We employed palladium allyl complexes in our investigations also because they are convenient starting compounds for the synthesis of Pd(0)-alkene species via reductive amination [6a, [16][17][18][19]; accordingly we report herein details on the synthesis of the new Pd(0) complex [Pd(g 2 -fumaronitrile)(Ph 2 PPy) 2 ] and on its protonation.…”

Section: Introductionmentioning

confidence: 99%

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Protonation of palladium(II)-allyl and palladium(0)-olefin complexes containing 2-pyridyldiphenylphosphine

Scrivanti¹,

Bertoldini²,

Beghetto³

et al. 2009

Journal of Organometallic Chemistry

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Section: Protonation Of Complexmentioning

confidence: 73%

Section: Methodsmentioning

confidence: 99%

Section: Protonation Of Complexmentioning

confidence: 95%

Section: Synthesis and Characterization Of The Palladium Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Protonation of palladium(II)-allyl and palladium(0)-olefin complexes containing 2-pyridyldiphenylphosphine

Scrivanti¹,

Bertoldini²,

Beghetto³

et al. 2009

Journal of Organometallic Chemistry

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Sterically Less‐Hindered Half‐Titanocene(IV) Phenoxides: Ancillary‐Ligand Effect on Mono‐, Bis‐, and Tris(2‐Alkyl‐/arylphenoxy) Titanium(IV) Chloride Complexes

Kim

et al. 2010

Chemistry A European J

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A series of mono-, bis-, and tris(phenoxy)-titanium(IV) chlorides of the type [Cp*Ti(2-R-PhO)(n)Cl(3-n)] (n=1-3; Cp*=pentamethylcyclopentadienyl) was prepared, in which R=Me, iPr, tBu, and Ph. The formation of each mono-, bis-, and tris(2-alkyl-/arylphenoxy) series was authenticated by structural studies on representative examples of the phenyl series including [Cp*Ti(2-Ph-PhO)Cl(2)] (1 PhCl2), [Cp*Ti(2-Ph-PhO)(2)Cl] (2 PhCl), and [Cp*Ti(2-Ph-PhO)(3)] (3 Ph). The metal-coordination geometry of each compound is best described as pseudotetrahedral with the Cp* ring and the 2-Ph-PhO and chloride ligands occupying three leg positions in a piano-stool geometry. The mean Ti-O distances, observed with an increasing number of 2-Ph-PhO groups, are 1.784(3), 1.802(4), and 1.799(3) A for 1 PhCl2, 2 PhCl, and 3 Ph, respectively. All four alkyl/aryl series with Me, iPr, tBu, and Ph substituents were tested for ethylene homopolymerization after activation with Ph(3)C(+)[B(C(6)F(5))(4)](-) and modified methyaluminoxane (7% aluminum in isopar E; mMAO-7) at 140 degrees C. The phenyl series showed much higher catalytic activity, which ranged from 43.2 and 65.4 kg (mmol of Ti x h)(-1), than the Me, iPr, and tBu series (19.2 and 36.6 kg (mmol of Ti x h)(-1)). Among the phenyl series, the bis(phenoxide) complex of 2 PhCl showed the highest activity of 65.4 kg (mmol of Ti x h)(-1). Therefore, the catalyst precursors of the phenyl series were examined by treating them with a variety of alkylating reagents, such as trimethylaluminum (TMA), triisobutylaluminum (TIBA), and methylaluminoxane (MAO). In all cases, 2 PhCl produced the most catalytically active alkylated species, [Cp*Ti(2-Ph--PhO)MeCl]. This enhancement was further supported by DFT calculations based on the simplified model with TMA.

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Synthesis, Characterization, Reactivity of η 3-allylPd(L)(X), Where X = Cl and L = Imidazolylphosphine and Their Application in Aryl Amination Reactions

et al. 2014

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Cationic palladium(II)-allyl-complexes containing 2-pyridyldiphenylphosphine: X-ray crystal structure of the binuclear complex [Pd(η3-2-Me-allyl)(μ-Ph2PPy)]2(BF4)2. Detection of an intramolecular C(allyl)–H⋯phenyl ring π-interaction

Cited by 13 publications

References 27 publications

Protonation of palladium(II)-allyl and palladium(0)-olefin complexes containing 2-pyridyldiphenylphosphine

Protonation of palladium(II)-allyl and palladium(0)-olefin complexes containing 2-pyridyldiphenylphosphine

Sterically Less‐Hindered Half‐Titanocene(IV) Phenoxides: Ancillary‐Ligand Effect on Mono‐, Bis‐, and Tris(2‐Alkyl‐/arylphenoxy) Titanium(IV) Chloride Complexes

Synthesis, Characterization, Reactivity of η 3-allylPd(L)(X), Where X = Cl and L = Imidazolylphosphine and Their Application in Aryl Amination Reactions

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