Citation: YE Hong-De, XU Bao-Hua, HU Jiu-Rong, YAN Hong. Cobalt(Ⅲ)-Mediated Intramolecular Coupling of B(3)/B(6) in CpCoS₂C₂B₁₀H₁₀ with Cp Ligand[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(7): 1447-1452. doi: 10.11862/CJIC.2015.200 shu

Cobalt(Ⅲ)-Mediated Intramolecular Coupling of B(3)/B(6) in CpCoS₂C₂B₁₀H₁₀ with Cp Ligand

YE Hong-De ^1,2,, ,
XU Bao-Hua ¹ ,
HU Jiu-Rong ² ,
YAN Hong ^1,,

1.
1 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;
2.
2 School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao, Jiangxi 334001, China

Corresponding author: YE Hong-De, YAN Hong,
Received Date: 29 March 2015
Available Online: 8 May 2015
Fund Project: 国家自然科学基金(No.21361022, 21261020) (No.21361022, 21261020)第54批中国博士后科学基金面上基金(No.2013M541640) (No.2013M541640)

Half-sandwich 16e complex CpCoS₂C₂B₁₀H₁₀ (Cp: cyclopentadienyl) (1) reacted with HC≡CCO₂Me in the presence of 2-methylpropanedithioic acid to generate compounds {(C₅H₄CoS₂C₂B₉H₉)(CH=CHCO₂Me)(Me₂C=CS₂H)} (2) and (Me₂C=CS₂H)₃Co (3). In 2, one S-Co bond of 1 was broken, and the S atom linked with the terminal acetylenyl carbon atom of the HC≡CCO₂Me. Meanwhile, the Co atom in 1 linked to the S atom in 2-methylpropanedithioic acid with covalent bond while linked to the SH unit with coordinative bond. One carbon atom of Cp ring linked to the B(3)/B(6) cite of the carborane cage. The H atom of the B(3)/B(6) cite migrated to the internal acetylenyl carbon atom to form a trans-ethylenic bond. The Co atom of 1 linked to three S atoms of three 2-methylpropanedithioic acid molecules with covalent bond, while linked to the other three SH units with coordinative bond. As a result, product 3 formed. Complexes 2 and 3 have been characterized by IR, NMR, elemental analysis, mass spectrum and single-crystal X-ray diffraction analysis.
- cobalt;carborane;ligand;couple
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Cobalt(Ⅲ)-Mediated Intramolecular Coupling of B(3)/B(6) in CpCoS₂C₂B₁₀H₁₀ with Cp Ligand