Cu(II)‐promoted cyclization of hydrazonophthalazine to triazolophthalazine; Synthesis and structure diversity of six novel Cu(II)‐triazolophthalazine complexes

Saied M. Soliman, Jörg Albering, Ayman El-Faham

Research output: Contribution to journalArticleResearchpeer-review

Abstract

A novel route for the synthesis of Cu(II)‐triazolophthalazine complexes using the Cu(II)‐promoted cyclization dehydrogenation reactions of hydrazonophthalazines under reflux was presented. Two hydrazonophthalazines were cyclized to the corresponding triazolophthalazine ligands, 3‐pyridin‐2‐yl‐3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazine (TPP) and 3‐(3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazin‐3‐yl)‐benzoic acid (TP3COOH), followed by in situ complexation with Cu(II) yielding six novel Cu(II)‐triazolophthalazine complexes depending on the reaction conditions. The molecular and supramolecular structures of the Cu(II)‐triazolophthalazine complexes were discussed. The metal sites have rectangular pyramidal geometry in the [Cu(TPP)Cl2]2; 1 and [Cu(TP3COOEt)Cl2(H2O)]2; 4 dinuclear complexes, distorted square planar in [Cu(TP3COOMe)2Cl2]; 3, [Cu(TP3COOH)2Cl2]; 5 and [Cu(TP3COOH)2Cl2]·H2O; 6 and a distorted octahedral in [Cu(TPP)(H2O)2(NO3)2]; 2. Hirshfeld analysis showed that the O…H, C…H, Cl…H (except TP3COOH and 2), N…H and π‐π stacking interactions are the most important intermolecular contacts. The π‐π stacking interactions are the maximum for TP3COOH and complex 6 with net C…C/C…N contacts of 19.4% and 15.4%, respectively. The orbital–orbital interaction energies of the Cu‐N/Cu‐Cl bonds correlated inversely with the corresponding Cu‐N/Cu‐Cl distances, respectively. The charge transfer processes between Cu(II) and ligand groups were also discussed. The charge densities of the Cu(II) centers are reduced to 0.663–0.995 e due to the interactions with the ligand groups coordinating it.
Original languageEnglish
Article numbere4992
Number of pages16
JournalApplied Organometallic Chemistry
Volume33
Issue number6
DOIs
Publication statusE-pub ahead of print - 2019

Keywords

  • Cu(II)-triazolophthalazine
  • cylization/dehydrogenation
  • density functional theory
  • Hirshfeld
  • hydrazonophthalazine

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Chemistry (miscellaneous)
  • Chemistry(all)

Fields of Expertise

  • Advanced Materials Science

Treatment code (Nähere Zuordnung)

  • Basic - Fundamental (Grundlagenforschung)

Cite this

Cu(II)‐promoted cyclization of hydrazonophthalazine to triazolophthalazine; Synthesis and structure diversity of six novel Cu(II)‐triazolophthalazine complexes. / Soliman, Saied M.; Albering, Jörg; El-Faham, Ayman.

In: Applied Organometallic Chemistry, Vol. 33, No. 6, e4992, 2019.

Research output: Contribution to journalArticleResearchpeer-review

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title = "Cu(II)‐promoted cyclization of hydrazonophthalazine to triazolophthalazine; Synthesis and structure diversity of six novel Cu(II)‐triazolophthalazine complexes",
abstract = "A novel route for the synthesis of Cu(II)‐triazolophthalazine complexes using the Cu(II)‐promoted cyclization dehydrogenation reactions of hydrazonophthalazines under reflux was presented. Two hydrazonophthalazines were cyclized to the corresponding triazolophthalazine ligands, 3‐pyridin‐2‐yl‐3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazine (TPP) and 3‐(3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazin‐3‐yl)‐benzoic acid (TP3COOH), followed by in situ complexation with Cu(II) yielding six novel Cu(II)‐triazolophthalazine complexes depending on the reaction conditions. The molecular and supramolecular structures of the Cu(II)‐triazolophthalazine complexes were discussed. The metal sites have rectangular pyramidal geometry in the [Cu(TPP)Cl2]2; 1 and [Cu(TP3COOEt)Cl2(H2O)]2; 4 dinuclear complexes, distorted square planar in [Cu(TP3COOMe)2Cl2]; 3, [Cu(TP3COOH)2Cl2]; 5 and [Cu(TP3COOH)2Cl2]·H2O; 6 and a distorted octahedral in [Cu(TPP)(H2O)2(NO3)2]; 2. Hirshfeld analysis showed that the O…H, C…H, Cl…H (except TP3COOH and 2), N…H and π‐π stacking interactions are the most important intermolecular contacts. The π‐π stacking interactions are the maximum for TP3COOH and complex 6 with net C…C/C…N contacts of 19.4{\%} and 15.4{\%}, respectively. The orbital–orbital interaction energies of the Cu‐N/Cu‐Cl bonds correlated inversely with the corresponding Cu‐N/Cu‐Cl distances, respectively. The charge transfer processes between Cu(II) and ligand groups were also discussed. The charge densities of the Cu(II) centers are reduced to 0.663–0.995 e due to the interactions with the ligand groups coordinating it.",
keywords = "copper complexes, crystal structure, novel Cu(II)‐triazolophthalazines, Cu(II)-triazolophthalazine, cylization/dehydrogenation, density functional theory, Hirshfeld, hydrazonophthalazine",
author = "Soliman, {Saied M.} and J{\"o}rg Albering and Ayman El-Faham",
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issn = "0268-2605",
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TY - JOUR

T1 - Cu(II)‐promoted cyclization of hydrazonophthalazine to triazolophthalazine; Synthesis and structure diversity of six novel Cu(II)‐triazolophthalazine complexes

AU - Soliman, Saied M.

AU - Albering, Jörg

AU - El-Faham, Ayman

PY - 2019

Y1 - 2019

N2 - A novel route for the synthesis of Cu(II)‐triazolophthalazine complexes using the Cu(II)‐promoted cyclization dehydrogenation reactions of hydrazonophthalazines under reflux was presented. Two hydrazonophthalazines were cyclized to the corresponding triazolophthalazine ligands, 3‐pyridin‐2‐yl‐3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazine (TPP) and 3‐(3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazin‐3‐yl)‐benzoic acid (TP3COOH), followed by in situ complexation with Cu(II) yielding six novel Cu(II)‐triazolophthalazine complexes depending on the reaction conditions. The molecular and supramolecular structures of the Cu(II)‐triazolophthalazine complexes were discussed. The metal sites have rectangular pyramidal geometry in the [Cu(TPP)Cl2]2; 1 and [Cu(TP3COOEt)Cl2(H2O)]2; 4 dinuclear complexes, distorted square planar in [Cu(TP3COOMe)2Cl2]; 3, [Cu(TP3COOH)2Cl2]; 5 and [Cu(TP3COOH)2Cl2]·H2O; 6 and a distorted octahedral in [Cu(TPP)(H2O)2(NO3)2]; 2. Hirshfeld analysis showed that the O…H, C…H, Cl…H (except TP3COOH and 2), N…H and π‐π stacking interactions are the most important intermolecular contacts. The π‐π stacking interactions are the maximum for TP3COOH and complex 6 with net C…C/C…N contacts of 19.4% and 15.4%, respectively. The orbital–orbital interaction energies of the Cu‐N/Cu‐Cl bonds correlated inversely with the corresponding Cu‐N/Cu‐Cl distances, respectively. The charge transfer processes between Cu(II) and ligand groups were also discussed. The charge densities of the Cu(II) centers are reduced to 0.663–0.995 e due to the interactions with the ligand groups coordinating it.

AB - A novel route for the synthesis of Cu(II)‐triazolophthalazine complexes using the Cu(II)‐promoted cyclization dehydrogenation reactions of hydrazonophthalazines under reflux was presented. Two hydrazonophthalazines were cyclized to the corresponding triazolophthalazine ligands, 3‐pyridin‐2‐yl‐3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazine (TPP) and 3‐(3,10b‐dihydro‐[1,2,4]triazolo[3,4‐a]phthalazin‐3‐yl)‐benzoic acid (TP3COOH), followed by in situ complexation with Cu(II) yielding six novel Cu(II)‐triazolophthalazine complexes depending on the reaction conditions. The molecular and supramolecular structures of the Cu(II)‐triazolophthalazine complexes were discussed. The metal sites have rectangular pyramidal geometry in the [Cu(TPP)Cl2]2; 1 and [Cu(TP3COOEt)Cl2(H2O)]2; 4 dinuclear complexes, distorted square planar in [Cu(TP3COOMe)2Cl2]; 3, [Cu(TP3COOH)2Cl2]; 5 and [Cu(TP3COOH)2Cl2]·H2O; 6 and a distorted octahedral in [Cu(TPP)(H2O)2(NO3)2]; 2. Hirshfeld analysis showed that the O…H, C…H, Cl…H (except TP3COOH and 2), N…H and π‐π stacking interactions are the most important intermolecular contacts. The π‐π stacking interactions are the maximum for TP3COOH and complex 6 with net C…C/C…N contacts of 19.4% and 15.4%, respectively. The orbital–orbital interaction energies of the Cu‐N/Cu‐Cl bonds correlated inversely with the corresponding Cu‐N/Cu‐Cl distances, respectively. The charge transfer processes between Cu(II) and ligand groups were also discussed. The charge densities of the Cu(II) centers are reduced to 0.663–0.995 e due to the interactions with the ligand groups coordinating it.

KW - copper complexes, crystal structure, novel Cu(II)‐triazolophthalazines

KW - Cu(II)-triazolophthalazine

KW - cylization/dehydrogenation

KW - density functional theory

KW - Hirshfeld

KW - hydrazonophthalazine

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U2 - 10.1002/aoc.4992

DO - 10.1002/aoc.4992

M3 - Article

VL - 33

JO - Applied Organometallic Chemistry

JF - Applied Organometallic Chemistry

SN - 0268-2605

IS - 6

M1 - e4992

ER -