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

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journal contribution
posted on 28.09.2015, 00:00 by Xiaoxia Gu, Lijun Zhang, Xiancui Zhu, Shaowu Wang, Shuangliu Zhou, Yun Wei, Guangchao Zhang, Xiaolong Mu, Zeming Huang, Dongjing Hong, Feng Zhang
The bis­(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes LRE­[N­(SiMe3)2]2 (L = 4-CH3-2-{R-[N­(CH)2CN]}­C6H3]2N; L2, R = CH3; L3, R = CH­(CH3)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 (H3L2I2) or bis­[2-(3-isopropylimidazolium)-4-methylphenyl]­amine diiodide (H3L3I2) with 5 equiv of NaN­(SiMe3)2 followed by treatment with 1 equiv of RECl3 in THF at −78 °C afforded the bis­(NHC)-based CNC-pincer rare-earth-metal amido complexes LRE­[N­(SiMe3)2]2 (L2 = [4-CH3-2-{CH3-[N­(CH)2CN]}­C6H3]2N, RE = Y (1), Eu (2), Er (3); L3 = [4-CH3-2-{(CH3)2CH-[N­(CH)2CN]}­C6H3]2N, RE = Y (4), Er (5), Yb (6)). Complexes 46 can also be prepared by stepwise reactions of H3L3I2 with n-BuLi in THF followed by reactions with [(Me3Si)2N]3RE­(μ-Cl)­Li­(THF)3. Stepwise reactions of H3L2I2 with n-BuLi in THF followed by treatment with [(Me3Si)2N]3RE­(μ-Cl)­Li­(THF)3 generated the bis­(NHC)-based CNC-pincer rare-earth-metal amido complexes L2RE­[N­(SiMe3)2]2 (RE = Y (1), Er (3)) together with the fused-heterocyclic compound 3,8,9-trimethyl-8a,9-dihydro-8H-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 LRE­[N­(SiMe3)2]2 by reaction of H3L3I2 with [(Me3Si)2N]3Yb­(μ-Cl)­Li­(THF)3 in THF, however, afforded mixed complexes of the bis­(NHC)-based CNC-pincer ytterbium complex L3Yb­[N­(SiMe3)2]2 (6) and the unexpected bis­(NHC)-based CNC-pincer monoamido ytterbium iodide L3YbI­[N­(SiMe3)2] (8). Investigation of the catalytic activity of complexes 16 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.