Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl

Abstract

The first insertion reaction of CO with a molecular complex of the heavy p-block elements is reported (principal quantum number > 4).

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

“…The importance of environmentally benign heavy element bismuth (Bi) in catalysis has come to the foreground in recent years with the electrochemical reduction of dinitrogen to ammonia and carbon dioxide to formate and homogenous catalysis involving fluorination of arenes . While these reactions utilize the redox active property of Bi, electrophilic activation of CO, CO 2 , and sp 2[9] and sp 3 C−H bonds by Bi III compounds in a stoichiometric manner has motivated chemists to explore ways to convert these to catalytic processes. Examples of catalytic reactions involving highly electrophilic Bi III are rare and such catalysts tend to react even with conventional solvents .…”

Bismuth Compounds in Radical Catalysis: Transition Metal Bismuthanes Facilitate Thermally Induced Cycloisomerizations

“…Hence, their existence was often suggested merely based on the analysis of stable diamagnetic products . Only recently, the first examples of well‐defined persistent or even isolable bismuth radical compounds have been reported . To date, the only catalytic application of an isolable bismuth radical is the dehydrogenative coupling of SiPhH 3 with TEMPO to give SiPhH 2 (TEMPO) (TEMPO=tetramethylpiperidinyl‐ N ‐oxide) .…”

“…[2,4,7] Only recently,the first examples of well-defined persistent [8] or even isolable bismuth radical compounds have been reported. [9][10][11] To date,the only catalytic application of an isolable bismuth radical is the dehydrogenative coupling of SiPhH 3 with TEMPO to give SiPhH 2 (TEMPO) (TEMPO = tetramethylpiperidinyl-N-oxide). [12,13] While of great fundamental significance,t he bismuth radical showed al ow cata-lytic activity (75 %conversion after 15 d) [14] and the use of the isolable radical TEMPO as as ubstrate was necessary to facilitate the reaction.…”

Squeezing Bi: PNP and P2N3 Pincer Complexes of Bismuth(III

“…including CH and CO activation and polymerization via activation of π systems and ethers. [58][59][60][61][62] In line with these reports, solution of 2c in THF rapidly turn into insoluble purple gels via catalytic ring-opening polymerization of the cyclic ether ( Figure S15, ESI).…”