A neutral germanium/phosphorus frustrated Lewis pair: Synthesis and reactivity

• Published in: Journal of organometallic chemistry 2021-12, Vol.954-955, p.122071, Article 122071
• Main Authors: Yang, Qian, Wang, Liliang, Li, Yinhuan, Zhou, Linqun, Li, Zhifang
• Format: Article
• Language: English
• Subjects: Cycloaddition; Frustrated Lewis pair; Germanium
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2021.122071

•A novel neutral Ge-based frustrated Lewis pair (Cl3GeCH2PtBu2) 1 was prepared.•The X-ray analysis of 1 shows the structure could act as an intramolecular FLPs.•1 exhibits high reactivity towards a series of small molecules. A novel germinal germanium/phosphorus frustrated Lewis pair, Cl3GeCH2PtBu21, was prepared through the metathesis reaction of tBu2PCH2Li with tetrachlorogermanium. This neutral germanium-based frustrated Lewis pair 1 exhibits higher reactivity toward a series of small molecules. When 1 was treated with an excess amount of tetrachloromethane (2.3equiv) yielding a zwitterionic adduct 2, Cl4GeCH2P(Cl)tBu2. The cycloaddition of dimethyl but-2-ynedioate with 1 was took place smoothly at room temperature, and afforded a zwitterionic cyclic vinyl 3 in good yields. The reaction of 1 with furan-2,5-dione has also been performed giving the corresponding cycloaddition 4 in high yields. The additions of C=Ch (Ch = O, and S) units involving 1-isocyanato-4-methylbenzene and isothiocyanatobenzene with 1 have been also carried out at ambient temperature in which the five-membered GeCPCO(S)-ring products 5a and 5b were furnished, respectively. All these above-mentioned compounds 1-5 were fully characterized by multinuclear NMR spectroscopy, high-resolution mass spectrometry (HRMS), and the structures of 1 and 3 were also determined by single-crystal X-ray diffraction. [Display omitted]