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Reference of 1038-95-5. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 1038-95-5, Name is Tri-p-tolylphosphine
The starting complex trans- is prepared from trans- by treatment of the derived labile solvento cationic species trans-BF4 (solv = acetone or CH2Cl2) with NaBH4 in EtOH at 0 dec C.The hydridotriflouromethyl complexes trans- are obtained by reaction of trans-PtH(CF3)(PPh3)2> with 2 equivalents of phosphine, L, in n-heptane at room temperature.Similar exchange reactions between trans- and equivalent amounts of diphosphine, L-L = cis-Ph2PCH=CHPPh2, Ph2PCH2CH2PPh2, Me2PCH2CH2PMe2, or Ph2PCH2CH2CH2PPh2, lead to the formation of the corresponding compounds.The hydridotrifluoromethyl complexes with L-L = cis-Ph2PCH=CHPPh2 and Ph2PCH2CH2PPh2 can be prepared also by reaction of the parent chloro derivatives with NaBH4 in EtOH at room temperature.The mixed isocyanide-phosphine complexes are obtained by reaction of trans- with a three-fold excess of RNC in n-heptane at room temperature.All the hydridotrilfluoromethyl complexes are air-stable in the solid state and in solution.They were characterized by elemental analyses and i.r., (1)H, (19)F, and (31)P n.m.r. spectra.The data obtained for upsilon(PtH) and (1)J(PtH) in trans- have been used to compare the trans influence of CF3(1-) with other ? carbon donors, R, in trans- derivatives.The n.m.r.-based trans influence order is CF3(1-) > C6H5(1-) > C6H9(1-) > CH2CH2CN(1-) > CH2CH2CH2CN(1-) > CH3(1-) > CH2CN(1-) > Cl(1-), whereas the i.r.-based trans influence order is C6H9(1-) > CH2CH2CH2CN(1-) > C6H5(1-) = CH3(1-) > CF3(1-) > Cl(1-).The opposite position of CF3(1-) in the two series of trans influence has been explained by the different mechanism operating on (1)J(PtH) and upsilon(PtH).The first depends predominantly on the s character of the platinum hydrid orbital used in the Pt-H bond, while the second is sensitive also to electrostatic effects induced by the electronegative fluorine atoms.The (1)J(PtP) data for the same series of complexes gives the following order of cis influence: Cl(1-) > CH2CN(1-) > CF3(1-) = CH3(1-) = C6H5(1-) = CH2CH2CN(1-) > CH2CH2CH2CN(1-).From the spectra of trans- (X = CF3 or Cl), the effects of replacing two PPh3 ligands in trans- by L on upsilon(PtH) and (1)J(PtH) were measured.With the assumption that the cis effects are additive, the i.r. and n.m.r. parameters were correlated with the electronic chi and steric theta parameters of the phosphine ligands.
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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate