Effect of the Additional Carboxyl Group in Half‐Sandwich Organometallic 2,4‐Dipicolinate Complexes on Solution Speciation and Structure | Zendy

Mészáros János P. | Zendy; Németi Gábor | Zendy; Poljarevic Jelena M. | Zendy; Holczbauer Tamás | Zendy; May Nóra V. | Zendy; Enyedy Éva A. | Zendy

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Effect of the Additional Carboxyl Group in Half‐Sandwich Organometallic 2,4‐Dipicolinate Complexes on Solution Speciation and Structure

Author(s) -

Mészáros János P.,

Németi Gábor,

Poljarevic Jelena M.,

Holczbauer Tamás,

May Nóra V.,

Enyedy Éva A.

Publication year - 2021

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.202100122

Subject(s) - chemistry , denticity , moiety , medicinal chemistry , bromide , carboxylate , toluene , picolinic acid , chloride , reactivity (psychology) , halide , inorganic chemistry , stereochemistry , crystallography , crystal structure , organic chemistry , medicine , alternative medicine , pathology

Solution speciation of Rh(η 5 ‐C 5 Me 5 ), Ru(η 6 ‐ p ‐cymene) and Ru(η 6 ‐toluene) complexes of 2,4‐pyridinedicarboxylic acid (2,4‐dipicH 2 ) was studied and compared to that of 2‐picolinic acid (picH) in addition to their reactivity towards chloride and bromide ions, 1‐methylimidazole and guanosine. Structures of [Rh(η 5 ‐C 5 Me 5 )(2,4‐dipicH)Cl] ⋅ 3H 2 O ( 1 ), 2[Ru(η 6 ‐toluene)(2,4‐dipicH)Cl] ⋅ 3H 2 O ( 2 ) and [Ru(η 6 ‐toluene)(2,4‐dipic)] 3 ⋅ 7H 2 O ( 3 ) were analyzed by X‐ray diffraction. 1 and 2 show typical piano stool geometry, while 3 is a triangular complex stabilized via the monodentate coordination of the second carboxylate group to the neighboring Ru(II) center. High stability [M(arene)L(H 2 O/Cl)] species predominate at pH 7.4. 2,4‐Dipic forms more stable complexes with Ru(η 6 ‐arene) than pic, with this difference being minor in the case of the Rh(η 5 ‐C 5 Me 5 ) complexes. A lower affinity of 2,4‐dipic complexes to halide ions was found compared to the corresponding pic complexes due to the additional COO − moiety.

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