Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile

Li, Jiancheng1,2; Wang, Xin-Feng1,2; Hu, Chaopeng1,2; Liu, Liu Leo1,2,3

2024-05-10

10.1021/jacs.4c04434

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Phosphagermylenylidenes (R-P & boxH;Ge), as heavier analogs of isonitriles, whether in their free state or as complexes with a Lewis base, have not been previously identified as isolable entities. In this study, we report the synthesis of a stable monomeric phosphagermylenylidene within the coordination sphere of a Lewis base under ambient conditions. This species was synthesized by Lewis base-induced dedimerization of a cyclic phosphagermylenylidene dimer or via Me3SiCl elimination from a phosphinochlorogermylene framework. The deliberate integration of a bulky, electropositive N-heterocyclic boryl group at the phosphorus site, combined with coordination stabilization by a cyclic (alkyl)(amino)carbene at the low-valent germanium site, effectively mitigated its natural tendency toward oligomerization. Structural analyses and theoretical calculations have demonstrated that this unprecedented species features a P & boxH;Ge double bond, characterized by conventional electron-sharing pi and sigma bonds, complemented by lone pairs at both the phosphorus and germanium atoms. Preliminary reactivity studies show that this base-stabilized phosphagermylenylidene demonstrates facile release of ligands at the Ge atom, coordination to silver through the lone pair on P, and versatile reactivity including both (cyclo)addition and cleavage of the P & boxH;Ge double bond.

SCI ; EI

英语

第一 ; 通讯

Guangdong Provincial Introduction of Innovative Research and Development Team["22301122","22350004","22101114","22271132"] ; National Natural Science Foundation of China["20231120110042001","JCYJ20220530114806015"] ; Shenzhen Science and Technology Innovation Program[2021ZT09C278]

Chemistry

Chemistry, Multidisciplinary

WOS:001225981200001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Coll Sci, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Coll Sci, Res Ctr Chem Biol & Omics Anal, Shenzhen 518055, Peoples R China
3.Nankai Univ, State Key Lab Elementoorgan Chem, Tianjin 300071, Peoples R China

Li, Jiancheng,Wang, Xin-Feng,Hu, Chaopeng,et al. Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(20).

Li, Jiancheng,Wang, Xin-Feng,Hu, Chaopeng,&Liu, Liu Leo.(2024).Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(20).

Li, Jiancheng,et al."Carbene-Stabilized Phosphagermylenylidene: A Heavier Analog of Isonitrile".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.20(2024).