Host-Guest Chemistry in Discrete Polyoxo-12-Palladate(II) Cubes [MO8Pd12L8]n- (M = ScIII, CoII, CuII, L = AsO43 -; M = CdII, HgII, L = PhAsO32-): Structure, Magnetism, and Catalytic Hydrogenation

Peng Yang; Mahmoud Elcheikh Mahmoud; Yixian Xiang; Zhengguo Lin; Xiang Ma; Jonathan H Christian; Jasleen K Bindra; Jared S Kinyon; Yue Zhao; Chaoqin Chen; Talha Nisar; Veit Wagner; Naresh S Dalal; Ulrich Kortz

doi:10.1021/acs.inorgchem.2c02751

Host-Guest Chemistry in Discrete Polyoxo-12-Palladate(II) Cubes [MO₈Pd₁₂L₈]^n- (M = Sc^III, Co^II, Cu^II, L = AsO₄^{3 -}; M = Cd^II, Hg^II, L = PhAsO₃^2-): Structure, Magnetism, and Catalytic Hydrogenation

Inorg Chem. 2022 Nov 21;61(46):18524-18535. doi: 10.1021/acs.inorgchem.2c02751. Epub 2022 Nov 7.

Authors

Peng Yang^{1

2}, Mahmoud Elcheikh Mahmoud¹, Yixian Xiang¹, Zhengguo Lin^{1

3}, Xiang Ma¹, Jonathan H Christian⁴, Jasleen K Bindra⁴, Jared S Kinyon⁴, Yue Zhao², Chaoqin Chen², Talha Nisar¹, Veit Wagner¹, Naresh S Dalal⁴, Ulrich Kortz¹

Affiliations

¹ School of Science, Jacobs University, Campus Ring 1, 28759 Bremen, Germany.
² College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, 410082 Changsha, P. R. China.
³ College of Chemistry and Materials Science, Hebei Normal University, 050024 Shijiazhuang, P. R. China.
⁴ Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.

PMID: 36342975
DOI: 10.1021/acs.inorgchem.2c02751

Abstract

A family of five host-guest assemblies comprising different metal ions inside a cuboid 12-palladium-oxo cage, [MO₈Pd₁₂L₈]^n- (MPd₁₂L₈, M = Sc^III, Co^II, Cu^II, L = AsO₄^3-; M = Cd^II, Hg^II, L = PhAsO₃^2-), was synthesized and structurally characterized in the solid state by single-crystal X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis, and their solution and gas-phase stability were validated by multinuclear NMR spectroscopy and electrospray-ionization mass spectrometry (ESI-MS). The polyoxopalladates (POPs) ScPd₁₂As₈, CoPd₁₂As₈, and CuPd₁₂As₈ represent the first three examples of the MPd₁₂As₈ archetype. The unique cubic ligand field of {MO₈} allows for collecting the speciation profiles of the POPs in solution using ⁴⁵Sc and ¹¹³Cd NMR techniques. Detailed magnetic and electron paramagnetic resonance (EPR) studies were performed on CuPd₁₂As₈. Catalytic studies on MPd₁₂As₈ (M = Cu^II and Co^II) supported on SBA-15 unveiled a guest metal-dependent structure-function relationship, with CuPd₁₂As₈ being the more efficient precatalyst for the hydroconversion of o-xylene in a fixed-bed reactor.