Synthesis and structural characterization of 2,2’-bipyridine zinc formate: Analysis of formate bonding and hydrosilylation of CO2 and carbonyl compounds

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry Pub Date : 2024-12-05 DOI:10.1016/j.jorganchem.2024.123471

Gonzalo Fernandez de la Mora, Aaron Loo, Ran Yan, Eshe Hummingbird, Gerard Parkin

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Abstract

The zinc formate compound (bipy)Zn(O₂CH)₂ is obtained via the reaction of Zn(O₂CH)₂ with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O₂CH)₂ may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO₂H and (ii) CO₂. The molecular structure of (bipy)Zn(O₂CH)₂ has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and κ¹-monodentate formate ligands. As such, the coordination environment of the zinc provides a contrast to the octahedral sites in the isomeric 4,4’-bipyridine counterpart, (bipy^4,4’)Zn(O₂CH)₂, and the aqua derivative, (bipy)Zn(O₂CH)₂(OH₂)·H₂O, both of which feature bridging formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O₂CH)₂ participates in hydrosilylation transformations involving CO₂ and carbonyl compounds, including (i) the reaction of CO₂ with (MeO)₃SiH to afford HCO₂Si(OMe)₃ and (ii) insertion of Ph₂CO, PhC(O)Me, Me₂CO and PhCHO into the Si–H bonds of PhSiH₃ to afford PhSi[OCH(R)R’]₃ via PhSiH₂[OCH(R)R’] and PhSiH[OCH(R)R’]₂.

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来源期刊

Journal of Organometallic Chemistry 化学-无机化学与核化学

CiteScore

4.40

自引率

8.70%

发文量

221

审稿时长

36 days

期刊介绍： The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds. Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome. The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.