144501-68-8Relevant academic research and scientific papers
Bismuth-based cyclic synthesis of 3,5-di-tert-butyl-4-hydroxybenzoic acid via the oxyarylcarboxy dianion, (O2CC6H2 tBu2O)2-
Kindra, Douglas R.,Evans, William J.
, p. 3052 - 3054 (2014)
3,5-Di-tert-butyl-4-hydroxybenzoic acid can be made under mild conditions in a cyclic process from carbon dioxide and 3,5-di-tert-butyl-4-phenol using bismuth-based C-H bond activation and CO2 insertion chemistry starting with the Bi3+ complex, Ar′BiCl2, of the NCN pincer ligand, Ar′ = 2,6-(Me2NCH2) 2C6H3. Complexes of the recently discovered oxyaryl dianion, (C6H2tBu2-3,5-O-4) 2-, and the oxyarylcarboxy dianion, [O2C(C 6H2tBu2-3,5-O-4)]2-, are intermediates in the process. Further studies of the oxyarylcarboxy dianion in Ar′Bi[O2C(C6H2tBu 2-3,5-O-4)-κ2O,O′], show that it undergoes decarboxylation upon reaction with I2 and it reacts with trimethylsilyl chloride to produce the trimethylsilyl ether of the trimethylsilyl ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid and the Ar′BiCl2 starting material.
Nitric oxide insertion reactivity with the bismuth-carbon bond: Formation of the oximate anion, [ON=(C6H2tBu2O)]-, from the oxyaryl dianion, (C6H2tBu2O)2-
Kindra, Douglas R.,Casely, Ian J.,Ziller, Joseph W.,Evans, William J.
, p. 15242 - 15247 (2014)
The first example of NO insertion into a Bi-C bond has been found in the direct reaction of NO with a Bi3+ complex of the unusual (C6H2tBu2-3,5-O-4)2- oxyaryl dianionic ligand, namely, Ar′Bi(C6H2tBu2-3,5-O-4) [Ar′=2,6-(Me2NCH2)2C6H3] (1). The oximate complexes [Ar′Bi(ONC6H2-3,5-tBu2-4-O)]2(μ-O) (3) and Ar′Bi(ONC6H2-3,5-tBu2-4-O)2 (4) were formed as a mixture, but can be isolated in pure form by reaction of NO with a Bi3+ complex of the [O2C(C6H2tBu2-3-5-O-4]2- oxyarylcarboxy dianion, namely, Ar′Bi-[O2C(C6H2tBu2-3-5-O-4)-κ2O,O′]. Reaction of 1 with Ph3CSNO gave an oximate product with (Ph3CS)1- as an ancillary ligand, (Ph3CS)(Ar′)Bi(ONC6H2-3,5-tBu2-4-O) (5).
Insertion of CO2 and COS into Bi-C bonds: Reactivity of a bismuth NCN pincer complex of an oxyaryl dianionic ligand, [2,6-(Me 2NCH2)2C6H3]Bi(C 6H2tBu2O)
Kindra, Douglas R.,Casely, Ian J.,Fieser, Megan E.,Ziller, Joseph W.,Furche, Filipp,Evans, William J.
, p. 7777 - 7787 (2013/07/19)
The reactivity of the unusual oxyaryl dianionic ligand, (C 6H2tBu2-3,5-O-4)2-, in the Bi3+ NCN pincer complex Ar′Bi(C6H 2tBu2-3,5-O-4), 1, [Ar′ = 2,6-(Me 2NCH2)2C6H3] has been explored with small molecule substrates and electrophiles. The first insertion reactions of CO2 and COS into Bi-C bonds are observed with this oxyaryl dianionic ligand complex. These reactions generate new dianions that have quinoidal character similar to the oxyaryl dianionic ligand in 1. The oxyarylcarboxy and oxyarylthiocarboxy dianionic ligands were identified by X-ray crystallography in Ar′Bi[O2C(C6H2 tBu2-3-5-O-4)-κ2O,O′], 2, and Ar′Bi[OSC(C6H2tBu2-3-5-O-4)- κ2O,S], 3, respectively. Silyl halides and pseudohalides, R3SiX (X = Cl, CN, N3; R = Me, Ph), react with 1 by attaching X to bismuth and R3Si to the oxyaryl oxygen to form Ar′Bi(X)(C6H2tBu2-3,5- OSiR3-4) complexes, a formal addition across five bonds. These react with additional R3SiX to generate Ar′BiX2 complexes and R3SiOC6H3tBu2-2,6. The reaction of 1 with I2 forms Ar′BiI2 and the coupled quinone, 3,3′,5,5′-tetra-tert-butyl-4,4′- diphenoquinone, by oxidative coupling.
