The influence of the position of double bonds of unsaturated carboxylic acids on the type of the resulting coordination polymers of palladium(I)

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For the first time in the coordination chemistry of palladium, a new class of palladium(I) polymers with unsaturated monocarboxylic acids obtained by the interaction of palladium(II) acetate Pd3(μ-MeCO2)6 with monocarboxylic 3-pentenoic and 4-pentenoic acids with a double bond not conjugated with the carboxyl group, cinnamic and crotonic acids with a double bond conjugated with the carboxyl group was isolated, and the interaction with a dicarboxylic acid (itaconic) with a double bond conjugated with only one carboxyl group, similar to cinnamic and crotonic acids, was studied. Analysis of the composition of eight newly synthesized compounds, as well as their IR, Raman and EPR spectra showed that the obtained coordination polymers of Pd(I) [Pd(RCOO)6]n with 3-pentenoic {[Pd(π-C5H7O2)] ∙ H2O}n and 4-pentenoic [Pd(π-C5H7O2) ∙ C5H8O2)]n acids are diamagnetic, and with cinnamic [Pd(C9H7O2)]n, crotonic {[Pd(C4H5O2)]H2O}n and itaconic {[Pd(C5H4O4)H2O] ∙ 2H2O}n acids they are paramagnetic. The backbone of the obtained polymers is formed by bridging carboxylate groups and Pd–Pd bonds. The completion of the coordination polyhedron in the case of complexes with 3- or 4-pentenoic acid is carried out by coordinating their double bond with palladium, in polymer complexes with cinnamic and crotonic acids - by the formed agostic bond, in complexes with itaconic acid - by a coordinated water molecule. According to EPR spectroscopy, the polymer with itaconic acid contains paramagnetic centers characterized by a content of 1018 spin/g of unpaired electrons stable for a year, which allows it to be considered as a precursor for the creation of heterogeneous catalysts with increased catalytic activity.

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I. Efimenko

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

编辑信件的主要联系方式.
Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

N. Ivanova

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

O. Erofeeva

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

N. Efimov

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

L. Demina

Frumkin Institute of Physical chemistry and Electrochemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

A. Averin

Frumkin Institute of Physical chemistry and Electrochemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

N. Simonenko

Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences

Email: ines@igic.ras.ru
俄罗斯联邦, Moscow, 119991

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2. Fig. 1. View of infinitely developing in two directions building block of Pd(I) coordination polymer with 3-pent (1).

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3. Fig. 2. Structure of Pd(II) complex with 3-pent (2).

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4. Fig. 3. Structure of Pd(II) complex with 4-pent (4).

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5. Fig. 4. View of infinitely developing in two directions building block of Pd(I) coordination polymers: a – with cin (5), b – fragment of the structure of agostic bond in Pd(I) coordination polymer with mole (6) with identity of its structure with 5.

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6. Fig. 5. View of infinitely developing in two directions block of Pd(I) coordination polymer with itak (7).

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7. Fig. 6. Structure of trinuclear complex of Pd(II) with itak (8).

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