TY - JOUR
T1 - Synthesis, crystal structure, Hirshfeld surface analysis, DFT calculations and characterization of 1,3-propanediylbis(triphenylphosphonium) monotribromide as brominating agent of double bonds and phenolic rings
AU - Nokhbeh, Seyed Reza
AU - Gholizadeh, Mostafa
AU - Salimi, Alireza
AU - Sparkes, Hazel A.
PY - 2020/4/15
Y1 - 2020/4/15
N2 - This paper presents synthesis and structural characterization of new members of phosphorus-based organic bromides. 1,3-Propanediylbis(triphenylphosphonium) dibromide I and 1,3-propanediylbis(triphenylphosphonium) monotribromide II, as a new brominating agent for double bonds and phenolic rings, were synthesized. 1H NMR, 13C NMR, 31P NMR, FT-IR, single crystal X-ray diffraction crystallography, differential scanning calorimetry, thermogravimetric analysis and differential thermal analysis were used to characterize these salts. Thermal and physicochemical stability, simple working up, non-toxicity in comparison to liquid bromine and high yield are some of the advantages of these salts. These salts have good solubility in organic solvents, such as methanol, ethanol, acetone, dichloromethane and THF. Crystallographic data showed that compound I crystallized in the monoclinic crystal system, in P21 space group and compound II crystallized in the monoclinic crystal system, in P21/c space group and one of the bromide ions was replaced by tribromide ion in II. The crystal packing structures of title compounds were stabilized by various intermolecular interactions, especially of the type C-H∙∙∙π contacts. The molecular Hirshfeld surface analysis and 2D fingerprint analysis revealed that the C∙∙∙H (30.4% for the compound I and 28.3% for compound II) contact, which was related to C-H∙∙∙π interactions, had the major contribution in the crystal architectures. To get more insight about molecular structures of titled compounds, DFT calculations were performed (energy, structural optimization and natural bond orbital analysis). Bromination of double bonds and phenolic rings was carried out to prove the ability of the tribromide salt to bromine such organic substrates.
AB - This paper presents synthesis and structural characterization of new members of phosphorus-based organic bromides. 1,3-Propanediylbis(triphenylphosphonium) dibromide I and 1,3-propanediylbis(triphenylphosphonium) monotribromide II, as a new brominating agent for double bonds and phenolic rings, were synthesized. 1H NMR, 13C NMR, 31P NMR, FT-IR, single crystal X-ray diffraction crystallography, differential scanning calorimetry, thermogravimetric analysis and differential thermal analysis were used to characterize these salts. Thermal and physicochemical stability, simple working up, non-toxicity in comparison to liquid bromine and high yield are some of the advantages of these salts. These salts have good solubility in organic solvents, such as methanol, ethanol, acetone, dichloromethane and THF. Crystallographic data showed that compound I crystallized in the monoclinic crystal system, in P21 space group and compound II crystallized in the monoclinic crystal system, in P21/c space group and one of the bromide ions was replaced by tribromide ion in II. The crystal packing structures of title compounds were stabilized by various intermolecular interactions, especially of the type C-H∙∙∙π contacts. The molecular Hirshfeld surface analysis and 2D fingerprint analysis revealed that the C∙∙∙H (30.4% for the compound I and 28.3% for compound II) contact, which was related to C-H∙∙∙π interactions, had the major contribution in the crystal architectures. To get more insight about molecular structures of titled compounds, DFT calculations were performed (energy, structural optimization and natural bond orbital analysis). Bromination of double bonds and phenolic rings was carried out to prove the ability of the tribromide salt to bromine such organic substrates.
KW - 2D fingerprint plots
KW - Brominating agent
KW - Density function theory calculations
KW - Hirshfeld surface analysis
KW - Phosphonium tribromide
KW - X-ray crystallography
UR - http://www.scopus.com/inward/record.url?scp=85077789436&partnerID=8YFLogxK
U2 - 10.1016/j.molstruc.2020.127700
DO - 10.1016/j.molstruc.2020.127700
M3 - Article (Academic Journal)
AN - SCOPUS:85077789436
VL - 1206
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
M1 - 127700
ER -