Isolable ArInH ₂ : Double Hydroindation Agent

ABSTRACT The reaction of the P,C,P ‐pincer indium(III) chloride ArInCl 2 with 2 eq. of K[BEt 3 H] provided crystalline monomeric indane ArInH 2 (1) (Ar = 2,6‐(tBu 2 PO) 2 C 6 H 3 ) bearing two terminal In─H bonds. Indane 1 is a multitalented reagent that serves as a reductant toward dichalcogenides (PhE) 2 giving ArIn(EPh) 2 (2E, E = S, Se, Te) or a hydride source in reaction with 4‐CF 3 ‐C 6 H 4 OH that gives mono‐ or disubstituted indium phenolates ArIn(H)(4‐CF 3 ‐C 6 H 4 O) (3), ArIn(4‐CF 3 ‐C 6 H 4 O) 2 (4) depending on stoichiometry. Most importantly, 1 is an unprecedented double hydroindation agent, as illustrated by its reactions with aldehydes 4‐R‐C 6 H 4 CHO (R = OMe, CF 3 , F) yielding ArIn(4‐R‐C 6 H 4 CH 2 O) 2 (5R) or ketene Ph 2 C═C═O providing ArIn(Ph 2 C═CH─O) 2 (6).