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Reactivity of a 16‐Electron CpCo Half‐Sandwich Complex Containing a Chelating 1,2‐Dicarba‐ closo ‐dodecaborane‐1,2‐diselenolate Ligand towards FcC(O)C≡CH
Author(s) -
Ye Hongde,
Bai Wenjun,
Xie Mingshi,
Li Yizhi,
Yan Hong
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100159
Subject(s) - chemistry , alkyne , reactivity (psychology) , cyclopentadienyl complex , carborane , ligand (biochemistry) , crystallography , stereochemistry , molecule , crystal structure , x ray crystallography , medicinal chemistry , catalysis , organic chemistry , diffraction , optics , medicine , biochemistry , physics , alternative medicine , receptor , pathology
The 16‐electron half‐sandwich complex CpCo(Se 2 C 2 B 10 H 10 ) ( 1 , Cp = cyclopentadienyl) reacts with FcC(O)C≡CH in CH 2 Cl 2 at ambient temperature to give [{FcC(O)CCH}(Se 2 C 2 B 10 H 10 )] ( 3 ) and [CpCo(Se 2 C 2 B 10 H 9 ){CH 2 CC(O)Fc}] ( 4 ). Complex 3 is generated by the alkyne addition to the 1,2‐dicarba‐ closo ‐dodecaborane‐1,2‐diselenolate ligand in 1 with the loss of the CpCo unit. In 4 , metal‐induced B–H activation occurs in the B(3)/B(6) position of carborane followed by the formation of a C–B bond. In MeOH the reaction leads to an unexpected product, [{FcC(O)CHCH}CpCo(Se 2 C 2 B 9 H 9 ){CH 2 CC(O)Fc}] ( 5 ), which contains two alkynes and a nido ‐C 2 B 9 cage. In MeOH, 4 can further react with the alkyne to give 5 . In the presence of silica, 4 loses the CpCo unit to afford [{FcC(O)CCH 2 }(Se 2 C 2 B 10 H 9 )] ( 6 ), which is a symmetrical molecule with the B–CH 2 unit retained. All of these complexes have been characterized by IR, NMR, elemental analysis, mass spectrum, and single‐crystal X‐ray diffraction analysis.