Ligand-Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies

N V Satyachand Harisomayajula; Bo-Han Wu; Duan-Yen Lu; Ting-Shen Kuo; I-Chia Chen; Yi-Chou Tsai

doi:10.1002/anie.201801955

Ligand-Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies

Angew Chem Int Ed Engl. 2018 Jul 26;57(31):9925-9929. doi: 10.1002/anie.201801955. Epub 2018 May 14.

Authors

N V Satyachand Harisomayajula¹, Bo-Han Wu¹, Duan-Yen Lu¹, Ting-Shen Kuo², I-Chia Chen¹, Yi-Chou Tsai¹

Affiliations

¹ Department of Chemistry and Frontier Research Center on Fundamental and Applied Sciences and Matters, National Tsing Hua University, 101, Sec. 2, Guang-Fu Road, Hsinchu, 300, Taiwan.
² Department of Chemistry, National (Taiwan) Normal University, 88, Sec. 4, Ting-Chow Rd, Taipei, 116, Taiwan.

PMID: 29704400
DOI: 10.1002/anie.201801955

Abstract

Synthesis and characterization of two dodecacopper(I) extended metal atom chains (EMAC) assembled by two hexadentate bis(pyridylamido)amidinate-supported hexacopper(I) string complexes (monomers) via the ligand-unsupported cuprophilicity are described. In addition to short unsupported Cu-Cu contacts, two hexacopper fragments in these two dodecacopper EMACs show a bent conformation based on X-ray crystallography. Compared with their THF-bound hexacopper(I) monomers and protonated ligands, these ligand-unsupported cuprophilic interactions are shown to be weak by Raman spectroscopy. DFT calculations suggest the ligand-unsupported cuprophilicity originate from weak attractive orbital interactions, and the strength is estimated to be 2.4 kcal mol^-1 .

Keywords: Raman spectroscopy; copper; cuprophilicity; metal atom chains; multi-nitrogen ligand.