Synthesis of Bis(NHC)-Based CNC-Pincer Rare-Earth-Metal Amido Complexes and Their Application for the Hydrophosphination of Heterocumulenes

Abstract

The bis(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes L RE[N(SiMe 3 ) 2 ] 2 ( L = 4-CH 3 -2-{R-[N(CH) 2 CN]}C 6 H 3 ] 2 N; L 2, R = CH 3; L 3, R = CH(CH 3 ) 2 ) were synthesized and characterized, and their catalytic activities toward hydrophosphination of heterocumulenes were developed. Reactions of bis[2-(3-methylimidazolium)-4-methylphenyl]amine diiodide (H 3 L 2 I 2 ) or bis[2-(3-isopropylimidazolium)-4-methylphenyl]amine diiodide (H 3 L 3 I 2 ) with 5 equiv of NaN(SiMe 3 ) 2 followed by treatment with 1 equiv of RECl 3 in THF at −78 °C afforded the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes L RE[N(SiMe 3 ) 2 ] 2 ( L 2 = [4-CH 3 -2-{CH 3 -[N(CH) 2 CN]}C 6 H 3 ] 2 N, RE = Y ( 1 ), Eu ( 2 ), Er ( 3 ); L 3 = [4-CH 3 -2-{(CH 3 ) 2 CH-[N(CH) 2 CN]}C 6 H 3 ] 2 N, RE = Y ( 4 ), Er ( 5 ), Yb ( 6 )). Complexes 4 – 6 can also be prepared by stepwise reactions of H 3 L 3 I 2 with n -BuLi in THF followed by reactions with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 . Stepwise reactions of H 3 L 2 I 2 with n -BuLi in THF followed by treatment with [(Me 3 Si) 2 N] 3 RE(μ-Cl)Li(THF) 3 generated the bis(NHC)-based CNC-pincer rare-earth-metal amido complexes L 2 RE[N(SiMe 3 ) 2 ] 2 (RE = Y ( 1 ), Er ( 3 )) together with the fused-heterocyclic compound 3,8,9-trimethyl-8a,9-dihydro-8 H -benzo[4,5]imidazo[2′,1′:2,3]imidazo[1,2- a ]imidazo[2,1- c ]quinoxaline ( 7 ), which formed through carbene C–C and C–N coupling. Attempts to prepare complexes of the type L RE[N(SiMe 3 ) 2 ] 2 by reaction of H 3 L 3 I 2 with [(Me 3 Si) 2 N] 3 Yb(μ-Cl)Li(THF) 3 in THF, however, afforded mixed complexes of the bis(NHC)-based CNC-pincer ytterbium complex L 3 Yb[N(SiMe 3 ) 2 ] 2 ( 6 ) and the unexpected bis(NHC)-based CNC-pincer monoamido ytterbium iodide L 3 YbI[N(SiMe 3 ) 2 ] ( 8 ). Investigation of the catalytic activity of complexes 1 – 6 and 8 indicated that all complexes displayed high activity toward the addition of the phosphine P–H bond to heterocumulenes, producing the corresponding phosphaguanidines, phosphaureas, and phosphathioureas, which represents the first example of bis(NHC)-based CNC-pincer type rare-earth-metal amido complexes as catalysts for the catalytic addition of the phosphine P–H bond to heterocumulenes with high efficiency in the presence of a low catalyst loading at room temperature.