Conversions of osmabenzyne and isoosmabenzene.
We report herein the first example of the conversion of metallabenzyne II and isometallabenzene III. The osmium hydride vinylidene complex 1 reacts with HC≡CCH(OEt)(2) to give osmabenzyne 3 via isoosmabenzene 2. Compound 3 exhibits high thermal stability in air. Nonetheless, nucleophilic attack at 3 provides isoosmabenzenes 4 a and 4 b, or opens the ring to produce 5 a and 5 b. We propose mechanisms to disclose the intrinsic connection between the six-membered metallacycles, and carry out DFT calculations to rationalize the regioselectivity of the nucleophilic addition reactions.
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, PR China.
Qianyi
Q
Zhao
Jun
J
Zhu
Zi-Ao
ZA
Huang
Xiao-Yu
XY
Cao
Haiping
H
Xia
D001554:Benzene / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D009992:Osmium / Q000737:chemistry*
D009942:Organometallic Compounds; D009992:Osmium; D001554:Benzene