Related Experiment Video
Updated: Oct 3, 2026

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Synthesis, Structure, and Reactivity of [Zr(6)Cl(18)H(5)](2)(-), the First Paramagnetic Species of Its Class
Linfeng Chen1, F. Albert Cotton
1Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, College Station, Texas 77843.
Abstract:
Reaction of [Zr(6)Cl(18)H(5)](3)(-) (1) with 1 equiv of TiCl(4) yields a new cluster anion, [Zr(6)Cl(18)H(5)](2)(-) (2), which can be converted back into [Zr(6)Cl(18)H(5)](3)(-) (1) upon addition of 1 equiv of Na/Hg. Cluster 2 is paramagnetic and unstable in the presence of donor molecules. It undergoes a disproportionation reaction to form 1, some Zr(IV) compounds, and H(2). It also reacts with TiCl(4) to form [Zr(2)Cl(9)](-) (4) and a tetranuclear mixed-metal species, [Zr(2)Ti(2)Cl(16)](2)(-) (3). The oxidation reaction of 1 with TiCl(4) is unique. Oxidation of 1 with H(+) in CH(2)Cl(2) solution results in the formation of [ZrCl(6)](2)(-) (5) and H(2), while in py solution the oxidation product is [ZrCl(5)(py)](-) (6). There is no reaction between 1 and TiI(4), ZrCl(4), [TiCl(6)](2)(-), [ZrCl(6)](2)(-), or CrCl(3). Compounds [Ph(4)P](2)[Zr(6)Cl(18)H(5)] (2a), [Ph(4)P](2)[Zr(2)Ti(2)Cl(16)] (3a), [Ph(4)P](2)[Zr(2)Cl(9)] (4a), [Ph(4)P](2)[ZrCl(6)].4MeCN (5a.4MeCN), and [Ph(4)P][ZrCl(5)(py)] (6a) were characterized by X-ray crystallography. Compound 2a crystallized in the trigonal space group R&thremacr; with cell dimensions (20 degrees C) of a = 28.546(3) Å, b = 28.546(3) Å, c = 27.679(2) Å, V = 19533(3) Å(3), and Z = 12. Compound 3a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 11.375(3) Å, b = 13.357(3) Å, c = 11.336(3) Å, alpha = 106.07(1) degrees, beta = 114.77(1) degrees, gamma = 88.50(1) degrees, V = 1494.8(7) Å(3), and Z = 1. Compound 4a crystallized in the triclinic space group P&onemacr; with cell dimensions (-60 degrees C) of a = 12.380(5) Å, b = 12.883(5) Å, c = 11.000(4) Å, alpha = 110.39(7) degrees, beta = 98.29(7) degrees, gamma = 73.12(4) degrees, V = 1572(1) Å(3), and Z = 2. Compound 5a.4MeCN crystallized in the monoclinic space group P2(1)/c with cell dimensions (-60 degrees C) of a = 9.595(1) Å, b = 19.566(3) Å, c = 15.049(1) Å, beta = 98.50(1) degrees, V = 2794.2(6) Å(3), and Z = 2. Compound 6a crystallized in the monoclinic space group P2(1)/c with cell dimensions (20 degrees C) of a = 10.3390(7) Å, b = 16.491(2) Å, c = 17.654(2) Å, beta = 91.542(6) degrees, V = 3026.4(5) Å(3), and Z = 4.
More Related Videos
08:15Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
12:43The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Related Concept Videos
Valence Bond Theory
Colors and Magnetism
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human eye.
Properties of Transition Metals
Ionic Bonding and Electron Transfer
Halogens
Ionic Crystal Structures
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...