Heterodimetallic PdII-based carboxylate-bridged complexes: Synthesis and structure of single-crystalline PdII–M (M = MnII, CoII, NiII, CuII, ZnII, NdIII, EuIII, CeIV) acetates

Kozitsyna, N. Yu.; Нефедов, С. Е.; Dolgushin, Fedor M.; Черкашина, Н. В.; Варгафтик, М. Н.; Моисеев, И. И.

doi:10.1016/j.ica.2006.01.027

Cited by 100 publications

(21 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Here, owing to the use of AcOH as reaction medium for hydration, the similar NMR characterization of the acetate ligand was not applicable, however, in UV/Vis studies, adding Sc(OTf) 3 to Pd(OAc) 2 in AcOH solution still revealed an increase in the Pd II absorbance band, which indicates the formation of the new Pd II species (see Figure S2 in the Supporting Information). More importantly, it has been well documented that adding bivalent or trivalent metal ions, including Ba 2+ , Sr 2+ , Ca 2+ , Mn 2+ , Co 2+ , Ni 2+ , Cd 2+ , Zn 2+ , Ce 3+ , Nd 3+ , Eu 3+ , and Ce 4+ , to the AcOH solution of Pd(OAc) 2 can lead to the formation of heterobimetallic Pd II species having an acetate bridge . Accordingly, a similar heterobimetallic Pd II /Sc III species with a diacetate bridge could be generated here and serves as the active catalyst for nitrile hydration through a “two‐metal‐ion mechanism” (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature

Zhang

Lou

et al. 2017

Eur J Org Chem

View full text Add to dashboard Cite

Transition‐metal‐catalyzed nitrile hydration is an atom‐economic method for the synthesis of various amides. This work demonstrates for the first time that the addition of non‐redox metal ions like Sc3+ dramatically accelerate the hydration of various nitriles to amides at ambient temperature with the simple Pd(OAc)2 salt as catalyst, whereas the reactions with Pd(OAc)2 alone were very sluggish. The formation of a heterobimetallic PdII/ScIII species has been proposed as the key species for the hydration that demonstrates a bimetallic synergistic effect in this process.

show abstract

Section: Resultsmentioning

confidence: 99%

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature

Zhang

Lou

et al. 2017

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…This distance is much shorter than those found in the crystal structures Pd 3 (OAc) 6 (av. 3.151(13) Å) and the other all‐acetate bridged hexamers (av. 3.4451(1) Å).…”

Section: Resultsmentioning

confidence: 99%

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

et al. 2017

View full text Add to dashboard Cite

Transition metal complexes derived from anionic polyimido ligands are very limited in the literature. Here we describe the deprotonation of alkyl substituted phosphoric triamides with bis(benzonitrile)palladium dichloride which results in the formation of chloro-bridged hexanuclear palladium(II) clusters of formula {Pd 3 [(NR) 3 PO](Cl) 3 } 2 in octahedral and prismatic geometries. These clusters consist of two trinuclear Pd 3 -motifs, each cis-protected by a tris(alkylimido)phosphate trianion, which are linked together by six m 2 -Cl bridges. A staggered arrangement of the two imido-Pd 3 units results in the formation of octahedral clusters (R = i Bu, n Bu, c Hex, i Pr and n Pr), while an eclipsed conformation (R = t Bu) gives rise to a prismatic cluster. A similar prismatic configuration was obtained for the mixedbridged clusters {Pd 3 [(NR) 3 PO](OAc) 2 (Cl)} 2 (R = c Hex and i Pr), formed in the reaction involving the corresponding phosphoric triamide, Pd(OAc) 2 and Pd(PhCN) 2 Cl 2 . The reaction of an octahedral cluster {Pd 3 [(N n Pr) 3 PO](Cl) 3 } 2 with 1,1'-ferrocene dicarboxylic acid (FDCÀH) gave the prismatic cluster {Pd 3 [(N n Pr) 3 PO](FDC)(Cl)} 2 which again consists of a mixed-bridged environment with FDC and Cl À linkers. Further, treatment of the octahedral {Pd 3 [(N n Pr) 3 PO](Cl) 3 } 2 cluster with i PrNH 2 , a stronger nucleophile, leads to its symmetric cleavage and forms the trinuclear cluster {Pd 3 [(NR) 3 PO]Cl 3 (R'NH 2 ) 3 }. We have also shown the catalytic activity of some of these Pd(II) complexes in the Suzuki reactions in both organic and aqueous phase conditions which suggest that all these imido-Pd(II) clusters are still suitable for catalytic reactions.

show abstract

“…A versatile approach towards synthesis of Pdcontaining acetate complexes with a general formula Pd(μ-OOCMe) 4 M(H 2 O) (M = Zn, Cu, Ni, Co, Mn) [17] or Pd 2 M 2 (μ,η 2 -OOCMe) 2 (μ-OOCMe) 8 (H 2 O) 2 ·(HOOCMe) 2 (M = Nd, Sm, Eu, Yb, Tm) [14] has been recently developed in the Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences (Moscow, Russia). These complexes can be used as precursors for bimetallic nanoparticles of a strictly defined composition.…”

Section: Introductionmentioning

confidence: 99%

Investigation into the Palladium‐Europium Acetate Reductive Decomposition with Synchrotron Radiation‐Based X‐ray Diffraction and X‐ray Absorption Spectroscopy

Khramov¹,

Belyakova²,

Murzin³

et al. 2014

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Abstract. The reductive decomposition of the complex Pd 2 Eu 2 (μ,η 2 -OOCMe) 2 (μ-OOCMe) 8 (H 2 O) 2 ·(HOOCMe) 2 upon heating from room temperature to 500°C in a hydrogen atmosphere was investigated by in situ synchrotron radiation-based X-ray absorption fine structure spectroscopy (XAFS) including observations of X-ray near-edge structure (XANES) and extended absorption fine structure (EXAFS) at Pd K-and Eu L 3 -edges and synchrotron X-ray diffraction (XRD). The Pd-Eu 2 O 3 nanocomposite was found to be the final thermolysis

show abstract

Heterodimetallic PdII-based carboxylate-bridged complexes: Synthesis and structure of single-crystalline PdII–M (M = MnII, CoII, NiII, CuII, ZnII, NdIII, EuIII, CeIV) acetates

Cited by 100 publications

References 18 publications

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

Investigation into the Palladium‐Europium Acetate Reductive Decomposition with Synchrotron Radiation‐Based X‐ray Diffraction and X‐ray Absorption Spectroscopy

Contact Info

Product

Resources

About

Heterodimetallic PdII-based carboxylate-bridged complexes: Synthesis and structure of single-crystalline PdII–M (M = MnII, CoII, NiII, CuII, ZnII, NdIII, EuIII, CeIV) acetates

Cited by 100 publications

References 18 publications

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)2/Lewis Acid Catalyst at Ambient Temperature

Chloro‐Bridged Hexanuclear Pd(II) Clusters Supported by cis‐Blocking Tris(imido)phosphate Trianions

Investigation into the Palladium‐Europium Acetate Reductive Decomposition with Synchrotron Radiation‐Based X‐ray Diffraction and X‐ray Absorption Spectroscopy

Contact Info

Product

Resources

About

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature

Efficient Bimetallic Catalysis of Nitrile Hydration to Amides with a Simple Pd(OAc)₂/Lewis Acid Catalyst at Ambient Temperature