Synthesis and Structure of Tetraphenylphosphorus, Tetraphenylantimony, and Tetraphenylbismuth Mesitylene Sulfonates Ph4EOSO2C6H2Me3-2,4,6 (E = P, Sb, Bi)

• Published in: Russian journal of inorganic chemistry Vol. 67; no. 12; pp. 1987 - 1992
• Main Authors: Sharutin, V. V., Sharutina, O. K., Senchurin, V. S., Krasnosel’skaya, V. V.
• Format: Journal Article
• Language: English
• Published: Moscow Pleiades Publishing 01-12-2022; Springer Nature B.V
• Subjects: Antimony; Antimony compounds; Benzene; Bismuth compounds; Chemistry; Chemistry and Materials Science; Coordination Compounds; Crystallography; Crystals; Inorganic Chemistry; Mesitylene; Sulfonates; Sulfonic acid; tetraphenylbismuth mesitylene sulfonate; synthesis; tetraphenylphosphorus; structure; tetraphenylantimony
• ISSN: 0036-0236; 1531-8613
• DOI: 10.1134/S0036023622601210

Tetraphenylphosphorus, tetraphenylantimony, and tetraphenylbismuth mesitylene sulfonates Ph
4
EOSO
2
C
6
H
2
Me
3
-2,4,6 (E = P (
I
), Sb (
II
), Bi (
III
)) have been synthesized in up to 91% yields by the reaction of equimolar amounts of pentaphenyl phosphorus, antimony, and bismuth compounds with mesitylene sulfonic acid in benzene. The crystal structures of these products have been determined by X-ray crystallography. Compounds
I
−
III
have also been synthesized from mesitylene sulfonic acid and tetraphenylphosphorus, tetraphenylantimony, and tetraphenylbismuth chlorides in water in up to 93% yields. Crystal
I
is composed of tetraphenylphosphonium cations (P−C, 1.7911(15)–1.7975(16) Å; CPC, 107.81(7)°–111.85(7)°) and mesitylene sulphonate anions (S−O, 1.4227(16)–1.4544(13) Å; OSO, 110.93(12)°–115.40(15)°). Compounds
II
and
III
are isostructural. The antimony and bismuth atoms in
II
and
III
have a distorted trigonal-bipyramidal coordination with the mesitylene sulfonate ligand in the axial position. The E−C
eq
bond lengths are 2.111(3)−2.124(3) Å
(II
) and 2.205(3)−2.213(3) Å (
III
); the E−C
ax
bond lengths are 2.144(3) and 2.237(3) Å, respectively; the СEO axial angles are 174.13(8)° and 173.47(9)°. The E−O distances (2.469(2) and 2.658(2) Å) exceed the sum of the covalent radii of the constituent atoms.