Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 865, Issue -, Pages 100-108Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2018.02.048
Keywords
B-phenylated o-carborane; LUMO energy stabilization; Electron withdrawing moiety; Chromium metal complexes; Pi-backbonding
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Funding
- Basic Science Research Program through the National Research Foundation of Korea (NRF) - Ministry of Education [2016R1D1A1B04933311]
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The electron accepting capability of B-phenylated o-carborane is greatly improved through favorable electronic interactions between the two adjoining phenyl-pi* and cage carbon-sigma* orbitals. Phenyl substitution at the boron atom in the 3-position directs the two phenyl groups of the cage carbon atoms to a face-to-face position and locks them into a rigid conformation, which gives rise to extensive electronic delocalization and maximum energy stabilization from the lowest unoccupied molecular orbital (LUMO). A reversible reduction peak from the cyclovoltammogram (CV) at -1.72 V and a broad and extended UV absorption (lambda(max) = 277 nm) substantiate such LUMO stabilization, thereby augmenting the electron accepting capability of o-carborane. Due to electron depletion from the adjacent o-carborane, the adjoined phenyl groups act as potential pi-acid; indeed, when B-phenylated 1,2-diphenyl-o-carborane was reacted with Cr(CO)(6), bi- and trimetallic chromium complexes were selectively formed in an eta(6)-bonding fashion between the chromium atoms and phenyl groups. (C) 2018 Elsevier B.V. All rights reserved.
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