Hypervalent organobismuth(iii) carbonate, chalcogenides and halides with the pendant arm ligands 2-(Me2NCH2)C6H4 and 2,6-(Me2NCH2)2C6H3

Abstract

R2BiOH (1) [R = 2-(Me2NCH2)C6H4] and (R2Bi)2O (2) are formed by hydrolysis of R2BiCl with KOH. Single crystals of were obtained by air oxidation of (R2Bi)2. The reaction of R2BiCl and Na2CO3 leads to (R2Bi)2CO3 (3). 3 is also formed by the absorption of CO2 from the air in solutions of 1 or 2 in diethyl ether or toluene. (R2Bi)2S (4) is obtained from R2BiCl and Na2S or from (R2Bi)2 and S8. Exchange reactions between R2BiCl and KBr or NaI give R2BiX [X = Br (5), I (6)]. The reaction of RBiCl2 (7) with Na2S and [W(CO)5(THF)] gives cyclo-(RBiS)2[W(CO)5]2 (8). cyclo-(R'BiS)2 (9) [R' = 2,6-(Me2NCH2)2C6H3] is formed by reaction of R'BiCl2 and Na2S. The structures of were determined by single-crystal X-ray diffraction.

A mini review on chemical fixation of CO2: Absorption and catalytic conversion into cyclic carbonates

“…The bismuth oxide 5 can be obtained by treating bismuth chloride 4a with aqueous sodium hydroxide. Analogous to the result of Breunig et al [30], bismuth hydroxide 4b readily loses water to form oxide 5. In turn, oxide 5 can be completely converted back to hydroxide 4b by adding water to it.…”

“…Despite inorganic Bi 2 O 3 is known to react with CO 2 [28,29], the use of bismuth compounds containing Bi-O bonds for CO 2 fixation has not been reported until very recently. Breunig et al [30] However, the authors did not mention whether carbonate 3 could transfer back to hydroxide 1 or oxide 2 or not.…”

“…Because methoxide 4c is sensitive to water, it undergoes hydrolysis and subsequent reaction Scheme 1 Adsorption of CO 2 by 1 or 2 [30] Scheme 2 Structure of 4 and 5 [16] Scheme 3 Adsorption of CO 2 by 4b or 5 [16] Scheme 4 Adsorption of CO 2 by 4c [16] with CO 2 to form a mixture of 4b, 5, and 6 in air. In an analogous manner, diorganobismuth oxide {(2,4,6-Me 3 C 6 H 2 ) 2 Bi} 2 O [31] was also found to show association ability with CO 2 by Yin et al The results suggest that the compound reacts reversibly with CO 2 , and the resulting carbonate is less stable than 6.…”

Synthesis and Characterization of Hypervalent Organoantimony(III) Compounds Containing the [2‐(Me2NCH2)C6H4]2Sb Fragment

“…[12] The Sb (1) [12] and (Me 2 Sb) 2 S [92.35(5)°]. [12] As observed for related [{2-(Me 2 NCH 2 )-C 6 H 4 } 2 Bi] 2 E (E = O, S), [22] in these µ-chalcogeno species the bridging chalcogen atoms apparently behave as clips pressing together the two "soft" metal atoms. The torsion angles φ (φ = Sb-E-Sb-lp; E = O, S, and lp assumed position of the lone pair of electrons at Sb) are 8.2°in 4 and 10.2°in 5, which is thus consistent with a syn-syn-conformation.…”

“…This folding induces planar chirality (with the aromatic ring and the nitrogen atom as chiral plane and pilot atom, respectively; isomers given as S N and R N ) [27] as described for other related main-group metal compounds. [9,10,22,[28][29][30][31][32][33] Indeed, all compounds crystallize as racemates, that is, the crystal is composed of discrete (R N1 ,S N2 ) and (S N1 ,R N2 ) isomers for 3, and (R N1 ,S N2 / R N1a ,S N2a ) and (S N1 ,R N2 /S N1a ,R N2a ) isomers for 4 and 5 (with respect to the two chelate rings at a metal center), respectively, with no unusual intermolecular distances shorter than the sum of the van der Waals radii between heavy atoms, or a heavy atom and H atoms.…”