Abstract
AbstractHeating (η‐C4H4BCy)Co(CO)2I (Cy = cyclohexyl) in benzene in the presence of AlCl3 and subsequent methanolysis affords the cationic benzene complex [(η‐C4H4BOMe)Co(η‐C6H6)]+ (1). Under visible‐light irradiation, 1 reacts with MeCN and tBuNC to give the tris(ligand) complexes [(η‐C4H4BOMe)Co(L)3]+ [L = MeCN (2), tBuNC (4)]. A similar reaction with P(OMe)3 in MeCN affords [(η‐C4H4BOMe)Co(MeCN){P(OMe)3}2]+ (5). Cation 2 reacts with BPh4– in CH2Cl2 to give the zwitterionic arene complex (η‐C4H4BOMe)Co(η‐C6H5BPh3) (3). Reactions of 2 with TlCp and Tl(η‐9‐SMe2‐7,8‐C2B9H10) afford the sandwich compounds (η‐C4H4BOMe)CoCp (6) and (η‐C4H4BOMe)Co(η‐9‐SMe2‐7,8‐C2B9H10) (7). The structures of 3 and 7 were determined by X‐ray diffraction. The bonding in the borole complexes [(C4H4BR)Co(C6H6)]+ and (C4H4BR)CoCp (R = H, OMe) was compared with that in the cyclobutadiene analogues [(C4R4)Co(C6H6)]+ and (C4R4)CoCp (R = H, Me) using energy decomposition analysis.
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