32461-51-1

Upstream product

• 6163-58-2 tris-(o-tolyl)phosphine 

Downstream Products

• 75503-50-3 Cd(SeP(C₆H₄CH₃)3)2(SP(C₆H₄CH₃)3)⁽²⁺⁾ 
• 75503-49-0 Cd(SeP(C₆H₄CH₃)3)(SP(C₆H₄CH₃)3)2⁽²⁺⁾ 

Relevant academic research and scientific papers

Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction

We report the first example of a silyl-Negishi reaction between secondary zinc organometallics and silicon electrophiles. This palladium-catalyzed process provides direct access to alkyl silanes. The delicate balance of steric and electronic parameters of the employed DrewPhos ligand is paramount to suppressing isomerization and promoting efficient and selective cross-coupling.

Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines and Their Application in the Copper-Free Cross-Coupling of Acid Chlorides and Terminal Alkynes

A practical synthesis yielding P-perfluoroalkylated phosphines from triarylphosphines and perfluoroalkyl iodides has been developed. The photoinduced reaction involves the substitution of aryl groups on the phosphorus atom with perfluoroalkyl groups to successfully afford P-perfluoroalkylated phosphines. In addition, the P-perfluoroalkylated phosphines were found to promote the Cu-free cross-coupling reaction of acid chlorides with terminal alkynes.

Rapid phosphorus(III) ligand evaluation utilising potassium selenocyanate

Oxidative addition of SeCN- to tertiary phosphine ligands has been investigated in methanol at 298 K by use of UV-Vis stopped-flow and conventional spectrophotometry. In most cases kobsvs. [SeCN -] plots were linear with zero intercepts corresponding to a rate expression of kobs = k1[SeCN-]. Reactions rates are dependent on the electron density of the phosphorus centre with k 1 varying by five orders of magnitude from 1.34 ± 0.02 × 10-3 to 51 ± 3 mol-1 dm3 s-1 for P(2-OMe-C6H4)3 to PCy3 respectively. Activation parameters range from 27 ± 1 to 49.0 ± 1.3 kJ mol-1 for ΔH? and -112 ± 9 to -140 ± 3 J K-1 mol-1 for ΔS ? supporting a SN2 mechanism in which the initial nucleophilic attack of P on Se is rate determining. Reaction rates are promoted by more polar solvents supporting the mechanistic assignment. Reasonable linear correlations were observed between log k1vs. pKa, 1JP-Se and χd values of the phosphines. The reaction rates are remarkably sensitive to the steric bulk of the substituents, and substitution of phenyl rings in the 2 position resulted in a decrease in the reaction rate. The crystal structures of SePPh2Cy and SePPhCy2 have been determined displaying Se-P bond distances of 2.111(2) and 2.1260(8) respectively. The Royal Society of Chemistry 2008.

Experimental and Theoretical Studies of Correlated Rotation in Tris(ortho-tolyl) Derivatives of P, As and Si

Variable temperature NMR studies have established equilibrium constants and/or activation parameters for the exo2 exo3 equilibrium in the series M(o-tolyl)3 (M=P, As), XM (o-tolyl)3 (M=P, X=O, S, Se; M=As, X=O, S) and n+ (n=O, M=Si; n=1, M=P, As).The crystal structure of OAs(o-tolyl)3H2O is reported.Molecular mechanics studies of P(o-tolyl)3 reproduce correctly the ground state exo3 conformation and provide an analysis of the lowest energy two-ring flip exchange mechanism.

STERIC AND ELECTRONIC DESTABILIZATION OF THE P-Se BOND IN TRIARYLPHOSPHINE SELENIDE SYSTEMS

Electronic and steric effects in SeP(Ar)3 compounds are discussed with the assistance of 1J(77Se-31P) correlations with d(P-Se) values and the pKa of the arylphosphines.