Polar self-assembly: steric effects leading to polar mixed-ligand coordination cages was written by Zhang, Jianyong;Miller, Philip W.;Nieuwenhuyzen, Mark;James, Stuart L.. And the article was included in Chemistry – A European Journal in 2006.Application In Synthesis of 2,2′,2”-(2,4,6-Trimethylbenzene-1,3,5-triyl)triacetonitrile The following contents are mentioned in the article:
The authors present a highly unusual example of self-assembly, specifically a polar, mixed-ligand cage which forms in preference to sym. homoligand products, and which suggests that steric effects can be exploited to obtain novel nonuniform polyhedral cages. In particular, reaction between the bulky tripodal triphosphine 2,4,6-tris(diphenylphosphino)triazine, L1, the nonbulky tripodal trinitrile 2,4,6-tris(cyanomethyl)trimethylbenzene, L2 and AgSbF6 in a 3:1:4 ratio gives the mixed-ligand aggregate [Ag4(L1)3(L2)(SbF6)]3+, 1-SbF6, instantly as the only product in quant. yield. The x-ray crystal structure of complex 1-SbF6 is consistent with the suspected solution-state structure. The cage derives from trigonal-pyramidal geometry, the basal vertexes of which are defined by three bulky triphosphines, L1, and the apical vertex by the nonbulky trinitrile, L2. There is apical elongation amounting to 19% in comparison to the ideal uniform tetrahedron. The cage also encapsulates an SbF6 anion. 19F NMR spectra in solution for the analogous PF6 complex [Ag4(L1)3(L2)(PF6)]3+, 1-PF6, confirm that one anion is also encapsulated in solution The synthesis of the analogous CF3SO3– complex, [Ag4(L1)3(L2)(OTf)]3+, 1-OTf, in solution is also described, although 1-PF6 and 1-OTf could not be isolated due to slow decomposition in solution The selective formation of these mixed-ligand cages is discussed in terms of ligand-ligand and ligand-included anion steric repulsions, which the authors propose prevent the formation of the competing hypothetical homoligand tetrahedral structure [Ag4(L1)4(SbF6)]3+, and thus favor the mixed ligand cage. Cage cone angles for L1 and L2 are estimated at 115° and 101°, resp. Variable-temperature 31P NMR spectroscopy shows that complex 1-SbF6 and the related previously reported partial tetrahedral complex [Ag4(L1)3(anion)]3+ undergo dynamic twisting processes in solution between enantiomeric C3-symmetry conformations. This study involved multiple reactions and reactants, such as 2,2′,2”-(2,4,6-Trimethylbenzene-1,3,5-triyl)triacetonitrile (cas: 16144-65-3Application In Synthesis of 2,2′,2”-(2,4,6-Trimethylbenzene-1,3,5-triyl)triacetonitrile).
2,2′,2”-(2,4,6-Trimethylbenzene-1,3,5-triyl)triacetonitrile (cas: 16144-65-3) belongs to nitriles. The R-C-N bond angle in and nitrile is 180° which give a nitrile functional group a linear shape. Both the carbon and the nitrogen are sp hydridized which leaves them both with two p orbitals which overlap to form the two π bond in the triple bond. Alkyl nitriles are sufficiently acidic to undergo deprotonation of the C-H bond adjacent to the CN group.Strong bases are required, such as lithium diisopropylamide and butyl lithium. The product is referred to as a nitrile anion. Application In Synthesis of 2,2′,2”-(2,4,6-Trimethylbenzene-1,3,5-triyl)triacetonitrile
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts