Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations.

ABSTRACT

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2 (LR )2 ] (R=H 1 a; R=CF3 1 b) combined with B(C6 F5 )3 (1 a/B(C6 F5 )3 , 1 b/B(C6 F5 )3 ) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H-H, Si-H and O-H bonds. Cleavage of H2 and Et3 SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR )2 ][HB(C6 F5 )3 ] (R=H 2 a; R=CF3 2 b) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2 O leads to [Mo(NtBu)(NHtBu)(LR )2 ][(HO)B(C6 F5 )3 ] (R=H 3 a; R=CF3 3 b). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a. Mechanistic elucidation revealed insertion of the aldehyde into the B-H bond of [HB(C6 F5 )3 ]- . We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR )2 ][{PhCH2 O}B(C6 F5 )3 ] (R=H 4 a; R=CF3 4 b). Catalysis occurs at [HB(C6 F5 )3 ]- while [Mo(NtBu)(NHtBu)(LR )2 ]+ (R=H or CF3 ) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).