We have applied crystal engineering as a tool to study the solid-state transformation from molecular salts to coordination complexes via mechanochemical dehydrochlorination reactions. The -(CH2)(n)- (n = 2, 3) alkyl chains were introduced into the bibenzylamine moiety to form the two nitrogen bases N,N,N',N'-tetrabenzylethylenediamine (L-1) and N,N,N',N'-tetrabenzylpropydiamine (L-2), which were self-assembled with tetrachlorometalates to form a series of supramolecular salts through second-sphere coordination. Single crystals of salts [L-1]2H(+)center dot[CuCl4](2-)center dot solvent (1) and [L-2]2H(+)center dot[XCl4](2-)center dot solvent (2-4; X = Cu, Hg, Zn) were obtained and their structures determined by single-crystal X-ray diffraction. The effect of different alkyl chains (two and three -CH2- units) on the solid-state reactivity showed that the chelating complexes resulting from the mechanochemical dehydrohalogenation reaction depend on the formation of quasi-chelating hydrogen-bonding salts. Quantum-mechanical calculations have been used to gain insight in this mechanocheinical dehydrohalogenation reaction, demonstrating that not only is size matching between reactants is important but also conformational energies, intermolecular interactions, and the symmetry of frontier molecular orbitals play an important role.

Synthesis of Chelating Complexes through Solid-State Dehydrochlorination Reactions via Second-Sphere-Coordination Interaction with Metal Chlorides: A Combined Experimental-Molecular Modeling Study

FAMULARI, ANTONINO
2014-01-01

Abstract

We have applied crystal engineering as a tool to study the solid-state transformation from molecular salts to coordination complexes via mechanochemical dehydrochlorination reactions. The -(CH2)(n)- (n = 2, 3) alkyl chains were introduced into the bibenzylamine moiety to form the two nitrogen bases N,N,N',N'-tetrabenzylethylenediamine (L-1) and N,N,N',N'-tetrabenzylpropydiamine (L-2), which were self-assembled with tetrachlorometalates to form a series of supramolecular salts through second-sphere coordination. Single crystals of salts [L-1]2H(+)center dot[CuCl4](2-)center dot solvent (1) and [L-2]2H(+)center dot[XCl4](2-)center dot solvent (2-4; X = Cu, Hg, Zn) were obtained and their structures determined by single-crystal X-ray diffraction. The effect of different alkyl chains (two and three -CH2- units) on the solid-state reactivity showed that the chelating complexes resulting from the mechanochemical dehydrohalogenation reaction depend on the formation of quasi-chelating hydrogen-bonding salts. Quantum-mechanical calculations have been used to gain insight in this mechanocheinical dehydrohalogenation reaction, demonstrating that not only is size matching between reactants is important but also conformational energies, intermolecular interactions, and the symmetry of frontier molecular orbitals play an important role.
2014
DENSITY-FUNCTIONAL THEORY, SPHERE COORDINATION CHEMISTRY, 2ND-SPHERE COORDINATION, BONDED NETWORKS, C-60 FULLERENE, CO-CRYSTALS, TRANSPORT, TECTONICS, POLYMERS, SALTS
File in questo prodotto:
File Dimensione Formato  
ic5007583.pdf

Accesso riservato

: Post-Print (DRAFT o Author’s Accepted Manuscript-AAM)
Dimensione 2.96 MB
Formato Adobe PDF
2.96 MB Adobe PDF   Visualizza/Apri
Synthesis of Chelating Complexes_11311-905156_Famulari.pdf

accesso aperto

: Post-Print (DRAFT o Author’s Accepted Manuscript-AAM)
Dimensione 2.73 MB
Formato Adobe PDF
2.73 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11311/905156
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 31
  • ???jsp.display-item.citation.isi??? 31
social impact