(Isocyano Group π-Hole)⋅⋅⋅[d z2 -M II] Interactions of (Isocyanide)[M II] Complexes, in which Positively Charged Metal Centers (d 8-M=Pt, Pd) Act as Nucleophiles

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Abstract

Inspection of the X-ray structures of the newly prepared trans-[M II(CNXyl) 2(DAPT) 2]Cl(BF 4) (M=Pd, Pt; Xyl=2,6-Me 2C 6H 3; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d 8-Pt II and d 8-Pd II metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d z 2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.

Original languageEnglish
JournalChemistry - A European Journal
DOIs
StateE-pub ahead of print - 1 Jan 2019

Keywords

  • density functional calculations
  • isocyanide ligands
  • metal interactions
  • noncovalent interactions
  • QTAIM calculations

Scopus subject areas

  • Inorganic Chemistry
  • Chemistry(all)
  • Catalysis
  • Organic Chemistry

Cite this

@article{03852341dbb24f9aa7390a86f05cf60b,
title = "(Isocyano Group π-Hole)⋅⋅⋅[d z2 -M II] Interactions of (Isocyanide)[M II] Complexes, in which Positively Charged Metal Centers (d 8-M=Pt, Pd) Act as Nucleophiles",
abstract = "Inspection of the X-ray structures of the newly prepared trans-[M II(CNXyl) 2(DAPT) 2]Cl(BF 4) (M=Pd, Pt; Xyl=2,6-Me 2C 6H 3; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d 8-Pt II and d 8-Pd II metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d z 2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.",
keywords = "density functional calculations, isocyanide ligands, metal interactions, noncovalent interactions, QTAIM calculations",
author = "S.A. Katkova and A.S. Mikherdov and M.A. Kinzhalov and A.S. Novikov and Золотарев, {Андрей Александрович} and V.P. Boyarskiy and Кукушкин, {Вадим Юрьевич}",
year = "2019",
month = "1",
day = "1",
doi = "10.1002/chem.201901187",
language = "English",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-Blackwell",

}

TY - JOUR

T1 - (Isocyano Group π-Hole)⋅⋅⋅[d z2 -M II] Interactions of (Isocyanide)[M II] Complexes, in which Positively Charged Metal Centers (d 8-M=Pt, Pd) Act as Nucleophiles

AU - Katkova, S.A.

AU - Mikherdov, A.S.

AU - Kinzhalov, M.A.

AU - Novikov, A.S.

AU - Золотарев, Андрей Александрович

AU - Boyarskiy, V.P.

AU - Кукушкин, Вадим Юрьевич

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Inspection of the X-ray structures of the newly prepared trans-[M II(CNXyl) 2(DAPT) 2]Cl(BF 4) (M=Pd, Pt; Xyl=2,6-Me 2C 6H 3; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d 8-Pt II and d 8-Pd II metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d z 2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.

AB - Inspection of the X-ray structures of the newly prepared trans-[M II(CNXyl) 2(DAPT) 2]Cl(BF 4) (M=Pd, Pt; Xyl=2,6-Me 2C 6H 3; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d 8-Pt II and d 8-Pd II metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d z 2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.

KW - density functional calculations

KW - isocyanide ligands

KW - metal interactions

KW - noncovalent interactions

KW - QTAIM calculations

UR - http://www.scopus.com/inward/record.url?scp=85066501582&partnerID=8YFLogxK

U2 - 10.1002/chem.201901187

DO - 10.1002/chem.201901187

M3 - Article

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

ER -