Cationic and neutral chloride complexes of palladium(II) with the nonaqueous solvent donors acetonitrile, dimethyl sulfoxide, and a series of amides. Mixed sulfur and oxygen coordination sites in a dimethyl sulfoxide complex

Wayland, Bradford B.; Schramm, Robert F.

doi:10.1021/ic50074a050

Cited by 172 publications

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“…Heating a solution of PdCl 2 in DMF at 100°C for 2 h resulted in the formation of a dark solid, which was identified as [PdCl 2 (DMF) 2 ]. This compound has already been prepared [44] by treating PdCl 2 with DMF at room temperature. However, upon dissolution in another solvent, this complex dissociates with loss of its two DMF ligands.…”

Section: Reactions Of K 2 Ptcl 4 Pdcl 2 and Na 2 Pdcl 6 With Dmfmentioning

confidence: 99%

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

Serp

Hernandez

Richard

et al. 2001

Eur. J. Inorg. Chem.

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Dimethyl formamide (DMF) can be a convenient source of the carbonyl ligand in the coordination chemistry of rhodium, ruthenium, iridium, and platinum. We have undertaken a thorough study concerning the course of this reaction. In a first step, DMF‐containing complexes are produced, which is usually accompanied by chloride redistribution. Then, upon refluxing, carbonyl species in the same oxidation state are obtained, presumably as a result of HCl‐mediated DMF decomposition. Provided that water levels are kept low, reduction can occur to provide the complexes [NH2(CH3)2][RhCl2(CO)2], [NH2(CH3)2][RuCl3(CO)2(DMF)], [RuCl2(CO)2(DMF)2], and [NH2(CH3)2][IrCl2(CO)2]. In the case of platinum, reduction is not effective and [NH2(CH3)2][PtCl3(CO)] is obtained. No carbonylpalladium species can be synthesized in this way, the reaction producing copious amounts of colloidal metal. Adding phosphanes to these chlorocarbonyl‐containing solutions allows easy, one‐step syntheses of a variety of complexes.

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Section: Reactions Of K 2 Ptcl 4 Pdcl 2 and Na 2 Pdcl 6 With Dmfmentioning

confidence: 99%

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

Serp

Hernandez

Richard

et al. 2001

Eur. J. Inorg. Chem.

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“…Data then corrected for Lorentz and polarization effects. Scattering factors of Cromer & Waber (1965) used and anomalousdispersion terms (Cromer, 1965) (Price et al, 1972) to be a cis-isomer with two S-bonded and two O-bonded Me2SO ligands similar to 4](C104) 2 (Wayland & Schramm, 1969). A proton NMR study in CH3NO 2 solution has shown that the O-bonded sulfoxides exchange rapidly with the free ligand while the S-bonded sulfoxides were kinetically stable.…”

Section: Synthesis and Structure Of Di-ct-hydroxo-bis[bis(dimethyl Sumentioning

confidence: 99%

Synthesis and structure of di-μ-hydroxo-bis[bis(dimethyl sulfoxide)platinum(II)] perchlorate

Rochon¹,

Kong²,

Melanson³

1985

Acta Crystallogr C

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“…[PdCl 2 (CH 3 CN) 2 ] (2) was purchased (Aldrich) or was prepared from PdCl 2 (Strem) employing a literature procedure. [32] An authentic sample of 2-carbomethoxycyclohexanone (5) was purchased from Fluka.…”

Section: Methodsmentioning

confidence: 99%

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

Han¹,

Wang²,

Pei³

et al. 2004

Chemistry A European J

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Reaction of 3-butenyl beta-keto esters or 3-butenyl alpha-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/CuCl2 in dioxane at 25-70 degrees C formed 2-substituted cyclohexanones in good yield with high regioselectivity. This protocol tolerated a number of ester and aryl groups and tolerated substitution at the allylic, enolic, and cis and trans terminal olefinic positions. In situ NMR experiments indicated that the chlorosilane was not directly involved in palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70 degrees C.

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Cationic and neutral chloride complexes of palladium(II) with the nonaqueous solvent donors acetonitrile, dimethyl sulfoxide, and a series of amides. Mixed sulfur and oxygen coordination sites in a dimethyl sulfoxide complex

Cited by 172 publications

References 0 publications

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

Synthesis and structure of di-μ-hydroxo-bis[bis(dimethyl sulfoxide)platinum(II)] perchlorate

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl

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Cationic and neutral chloride complexes of palladium(II) with the nonaqueous solvent donors acetonitrile, dimethyl sulfoxide, and a series of amides. Mixed sulfur and oxygen coordination sites in a dimethyl sulfoxide complex

Cited by 172 publications

References 0 publications

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

Synthesis and structure of di-μ-hydroxo-bis[bis(dimethyl sulfoxide)platinum(II)] perchlorate

Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me3SiCl or HCl

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Palladium‐Catalyzed Intramolecular Hydroalkylation of Alkenyl‐ β‐Keto Esters, α‐Aryl Ketones, and Alkyl Ketones in the Presence of Me₃SiCl or HCl