24059-61-8Relevant academic research and scientific papers
NON-METAL DERIVATIVES OF THE BULKIEST KNOWN TERTIARY PHOSPHINE, TRIMESITYLPHOSPHINE
Alyea, Elmer C.,Malito, John
, p. 175 - 182 (2007/10/02)
Trimesitylphosphine (Pmes3) is the bulkiest known tertiary phosphine.The low yield synthesis of this known compound, its failure to form a carbon disulfide adduct or a selenide derivative, the relatively low values for ν(P-O), ν(P-S) and ν(P-H) in its oxide, sulfide and phosphonium salt respectively, and the high barriers to rotation about the P-Cipso bond in Pmes3, and its derivatives all attest to this fact.Nevertheless, Pmes3, does show chemistry typical of most tertiary phosphines due to its relatively high basicity and the electronic character of even this most bulky phosphine must also be considered in any discussion of its chemistry.Key words: Tertiary phosphine; triaryl phosphine; steric effect; electronic effect.
Restricted Rotation in Methyl- and Cyanomethyl-tris-(2,4,6-trimethyl-phenyl)phosphonium Compounds. A 1H Nuclear Magnetic Resonance Spectroscopic Study. The Crystal Structure of Cyanomethyltris-(2,4,6-trimethylphenyl)phosphonium Tetraiodomercurate(II)
Bellamy, Anthony J.,Gould, Robert O.,Walkinshaw, Malcolm D.
, p. 1099 - 1104 (2007/10/02)
The crystal structure of cyanomethyltris-(2,4,6-trimethylphenyl)phosphonium tetraiodomercurate(II), 2*HgI4(2-), is reported, and the bonding and conformational characteristics of the cation are compared with those related structures wich also exist in a propeller conformation.The dynamic stereochemistry of Mes3P(1+)CH2CN, Mes3P(1+)CH3, and Mes3P, as studied by 1H n.m.r. spectroscopy, is described.The calculated ΔG++ values for enantiomerisation of the propeller configuration, assumed to occur via the two-ring flip mechanism, are discussed in the context of related studies.For Mes3P(1+)CH2CN, the enantiomerisation mechanism is related to the conformation in the crystalline state.
