Organopalladium-komplexe mit palladium in der oxidationsstufe + IV werden durch tripodale sauerstoffliganden stabilisiert

Kläui, Wolfgang; Glaum, Marcus; Wagner, Trixie; Bennett, Martin A.

doi:10.1016/0022-328x(94)80222-x

Cited by 25 publications

(16 citation statements)

References 14 publications

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“…[19] The explanation for this trend is attributed to the softer acidity of platinum compared with palladium. Steric influences on the trends in bond lengths, which were previously suggested as having an additional effect, [16,17] were eliminated after similar trends were found in the optimised geometries of trans-[M(H) 2 (CH 3 )(NH 3 )] -. [19] The five-membered chelate ring formed by the bidentate ligand in both the palladium and the platinum complexes is puckered, with the sulfur atom lying out of the M, N, C(2), C (21) The catalytic activity of [PdCl 2 L] in the Heck reaction was investigated.…”

Section: Structures Of [Pdcl 2 L 2 ] (2a) and [Ptcl 2 L 2 ] (2b)mentioning

confidence: 94%

Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)

et al. 2005

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Section: Structures Of [Pdcl 2 L 2 ] (2a) and [Ptcl 2 L 2 ] (2b)mentioning

confidence: 94%

Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)

et al. 2005

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“…[PdMe 3 (2,2Ј-bipy)(Et 3 [12]aneP 3 )]- Three platinum() complexes were prepared for comparison of spectra with those of palladium() complexes. The platinum() complexes are stable at ambient temperature and exhibit 1 H and 31 P NMR spectra similar to those of palladium() analogues, together with additional features associated with coupling involving the 195 Pt nucleus (Table 1, Fig.…”

Section: Synthesis and Characterisation Of Complexesmentioning

confidence: 99%

“…7 We report here the first isolation and structural determination for an organopalladium() phosphine complex, [PdMe 3 (phen)(PMe 2 Ph)][O 3 SCF 3 ] (phen = 1,10phenanthroline), characterisation of several palladium() and † Electronic supplementary information (ESI) available: NMR data for palladium-() and -() complexes. See http://www.rsc.org/suppdata/dt/ b0/b004741o/ platinum() analogues, a structural analysis of [PdMe(2,2Јbipy)(PMe 2 Ph)][O 3 SCF 3 ] formed on reductive elimination of ethane from a palladium() complex, and the further development of this chemistry to include the cyclic phosphine syn,syn-1,5,9-triethyl-1,5,9-triphosphacyclodecane (syn,syn-Et 3 [12]aneP 3 ).…”

Section: Introductionmentioning

confidence: 99%

Trimethyl-palladium(IV) and -platinum(IV) complexes containing phosphine donor ligands, including studies of 1,5,9-triethyl-1,5,9-triphosphacyclodecane and X-ray structural studies of palladium(II) and palladium(IV) complexes †

Bayler

Canty

Edwards

et al. 2000

J. Chem. Soc., Dalton Trans.

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“…Nevertheless, the oxidative addition of these Pd II –L OMe complexes has not been reported. The trialkyl–Pd IV complexes [(L OMe )Pd(Me) 2 R] were obtained by oxidative addition of [Pd(bpy)Me 2 ] (bpy = 2,2′‐bipyridine) with RI in the presence of [NaL Ome ]/[AgL Ome ]; however, like other trialkyl–Pd IV complexes, [(L OMe )Pd(Me) 2 R] do not undergo reductive elimination. To enhance the reactivity of the Pd IV center, we sought to synthesize monoaryl–Pd IV –L OEt halide complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

Au-yeung

Sung

et al. 2017

Eur J Inorg Chem

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Cationic monoaryl-Pd IV complexes supported by the Kläui tripodal ligand [Co(η 5 -C 5 H 5 ){P(O)(OEt) 2 } 3 ] -(L OEt -) were synthesized, and their reductive elimination was studied. Treatment of trans-[Pd(PPh 3 ) 2 (Ar)(I)] and [{Pd(η 2 -ppytBu)Cl} 2 ] [ppyt-BuH = 2-(4-tert-butylphenyl)pyridine] with [AgL OEt ] afforded [Pd(Ar)(PPh 3 )(η 2 -L OEt )] [Ar = Ph (1), p-tolyl (2)] and [Pd(η 2 -ppytBu)(η 2 -L OEt )] (3), respectively. 2928 (L OEt )](PF 6 ) (6), respectively. Complexes 4 and 5 underwent C(sp 2 )-Cl elimination at 40°C in acetonitrile to give a Pd II -L OEt species and the corresponding chloroarene. On the other hand, the C(sp 2 )-Cl elimination of 6 occurred at room temperature and afforded a Pd II species, presumably [Pd(ClppytBuH)-(L OEt )](PF 6 ), which further reacted with PhICl 2 to yield [Pd-(η 2 -ClppytBu)Cl(L OEt )](PF 6 ) (7) [ClppytBuH = 2-(4-tert-butyl-2chlorophenyl)pyridine]. The structures of complexes 1, 4, 6, and 7 were established by X-ray crystallography.Despite the wealth of organometallic chemistry of Pd 0 and Pd II , [5] the coligand effect on the reactivity of Pd IV complexes has not been well explored. Chelating coligands can increase the electron density of the Pd center, and thus facilitate Pd II / Pd IV oxidation and enhance the chemo-and regioselectivity of Pd-mediated C-H transformations. Of special interest are facially coordinating tridentate ligands, which have proven to be excellent spectator ligands for Pd IV . [2] Although Pd-based catalysts in oxygen-rich ligand environments [e.g., palladium(II) acetate and oxide] are well known, [1,6] not many well-defined organo-Pd IV complexes with O-donor ligands have been synthesized; [7] reported Pd IV complexes are mostly supported by N-and C-donor ligands. [2,8] We are particularly interested in Kläui's tripodal ligand [CoCp{P(O)(OEt) 2 } 3 ] -(Cp = η 5 -C 5 H 5 ; denoted L OEt hereafter; Scheme 2), which is capable of stabilizing metal ions in high oxidation states. [9] The synthesis of stable high-valent transition metal (e.g., Ru VI ), [9b,10a-10d] and lanthanide (Ce IV ) [10e] complexes of L OEt suggests that the {PdL OEt } fragment can serve as a good platform for the study of Pd IV organometallic chemistry. Previously, Kläui and co-workers synthesized Pd II complexes with bidentate L OR -(R = Me, Et) ligands, for example, [(η 2 -L OMe )Pd(allyl)] and [(η 2 -L OMe )Pd(PPh 3 )Cl]. [11] Nevertheless, the oxidative addition of these Pd II -L OMe complexes has not been reported. The trialkyl-Pd IV complexes [(L OMe )Pd(Me) 2 R] were obtained by oxidative addition of [Pd(bpy)Me 2 ] (bpy = 2,2′-bipyridine) with RI in the presence of [NaL Ome ]/[AgL Ome ]; [12] however, like other trialkyl-Pd IV complexes, [(L OMe )Pd(Me) 2 R] do not undergo reductive elimination. To enhance the reactivity of the Pd IV center, we sought to synthesize monoaryl-Pd IV -L OEt halide complexes. Herein, we describe the synthesis of cationic Pd IV -L OEt aryl com-Eur.

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Organopalladium-komplexe mit palladium in der oxidationsstufe + IV werden durch tripodale sauerstoffliganden stabilisiert

Cited by 25 publications

References 14 publications

Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)

Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)

Trimethyl-palladium(IV) and -platinum(IV) complexes containing phosphine donor ligands, including studies of 1,5,9-triethyl-1,5,9-triphosphacyclodecane and X-ray structural studies of palladium(II) and palladium(IV) complexes †

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

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Organopalladium-komplexe mit palladium in der oxidationsstufe + IV werden durch tripodale sauerstoffliganden stabilisiert

Cited by 25 publications

References 14 publications

Solution, Structural and Catalytic Studies of Neutral MCl2 (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH2)C5H4N(RE = MeS, PhS, MeSe)

Solution, Structural and Catalytic Studies of Neutral MCl2 (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH2)C5H4N(RE = MeS, PhS, MeSe)

Trimethyl-palladium(IV) and -platinum(IV) complexes containing phosphine donor ligands, including studies of 1,5,9-triethyl-1,5,9-triphosphacyclodecane and X-ray structural studies of palladium(II) and palladium(IV) complexes †

Synthesis, Structure, and Reductive Elimination of Cationic Monoarylpalladium(IV) Complexes Supported by a Tripodal Oxygen Ligand

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Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)

Solution, Structural and Catalytic Studies of Neutral MCl₂ (M = Pd, Pt) Complexes of the N/E Mixed‐Donor Ligands 2‐(RECH₂)C₅H₄N(RE = MeS, PhS, MeSe)