Abstract

The reaction of cis-[PdCl2(CNCy)2] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{C(N(H)4,5-R2-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R2-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH2)4- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl2{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC6H4(7), 4-FC6H4(8), 4-ClC6H4(9), 3,4-F2C6H3(10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ(S,N-H)Cl and also PdII···PdIImetallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ(S,N-H)Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl3solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS,1H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ(S,E-H)Cl systems were classified accordingly to E (E = N, O, C) type atoms.

Original languageEnglish
Pages (from-to)3420-3433
Number of pages14
JournalInorganic Chemistry
Volume57
Issue number6
DOIs
Publication statusPublished - 19 Mar 2018

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Chalcogens
Dimerization
carbenes
dimerization
halides
Amines
Hydrogen bonds
amines
hydrogen bonds
Discrete Fourier transforms
Nuclear magnetic resonance
nuclear magnetic resonance
Electronic density of states
Surface analysis
interactions
density distribution
solid phases
inspection
diffusion coefficient
Inspection

Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{ff350c635f114feb96c1788d69f5fcc5,
title = "Halides Held by Bifurcated Chalcogen-Hydrogen Bonds. Effect of μ (S,N-H)Cl Contacts on Dimerization of Cl(carbene)Pd II Species",
abstract = "The reaction of cis-[PdCl2(CNCy)2] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{C(N(H)4,5-R2-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91{\%}) in the case of 4,5-R2-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH2)4- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl2{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93{\%}) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC6H4(7), 4-FC6H4(8), 4-ClC6H4(9), 3,4-F2C6H3(10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ(S,N-H)Cl and also PdII···PdIImetallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ(S,N-H)Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl3solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS,1H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ(S,E-H)Cl systems were classified accordingly to E (E = N, O, C) type atoms.",
keywords = "Journal Article, POLARIZABLE CONTINUUM MODEL, HALOGEN-BOND, TETREL BONDING INTERACTIONS, X-RAY, DIAMINOCARBENE COMPLEXES, NONCOVALENT INTERACTIONS, ANION RECOGNITION, ACYCLIC DIAMINOCARBENES, SUPRAMOLECULAR CHEMISTRY, THEORETICAL INVESTIGATIONS",
author = "Mikherdov, {Alexander S.} and Novikov, {Alexander S} and Kinzhalov, {Mikhail A} and Boyarskiy, {Vadim P} and Starova, {Galina L} and Ivanov, {Alexander Yu} and Kukushkin, {Vadim Yu}",
note = "doi: 10.1021/acs.inorgchem.8b00190",
year = "2018",
month = "3",
day = "19",
doi = "10.1021/acs.inorgchem.8b00190",
language = "English",
volume = "57",
pages = "3420--3433",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Halides Held by Bifurcated Chalcogen-Hydrogen Bonds. Effect of μ (S,N-H)Cl Contacts on Dimerization of Cl(carbene)Pd II Species

AU - Mikherdov, Alexander S.

AU - Novikov, Alexander S

AU - Kinzhalov, Mikhail A

AU - Boyarskiy, Vadim P

AU - Starova, Galina L

AU - Ivanov, Alexander Yu

AU - Kukushkin, Vadim Yu

N1 - doi: 10.1021/acs.inorgchem.8b00190

PY - 2018/3/19

Y1 - 2018/3/19

N2 - The reaction of cis-[PdCl2(CNCy)2] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{C(N(H)4,5-R2-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R2-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH2)4- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl2{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC6H4(7), 4-FC6H4(8), 4-ClC6H4(9), 3,4-F2C6H3(10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ(S,N-H)Cl and also PdII···PdIImetallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ(S,N-H)Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl3solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS,1H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ(S,E-H)Cl systems were classified accordingly to E (E = N, O, C) type atoms.

AB - The reaction of cis-[PdCl2(CNCy)2] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{C(N(H)4,5-R2-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R2-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH2)4- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl2{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC6H4(7), 4-FC6H4(8), 4-ClC6H4(9), 3,4-F2C6H3(10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ(S,N-H)Cl and also PdII···PdIImetallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ(S,N-H)Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl3solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS,1H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ(S,E-H)Cl systems were classified accordingly to E (E = N, O, C) type atoms.

KW - Journal Article

KW - POLARIZABLE CONTINUUM MODEL

KW - HALOGEN-BOND

KW - TETREL BONDING INTERACTIONS

KW - X-RAY

KW - DIAMINOCARBENE COMPLEXES

KW - NONCOVALENT INTERACTIONS

KW - ANION RECOGNITION

KW - ACYCLIC DIAMINOCARBENES

KW - SUPRAMOLECULAR CHEMISTRY

KW - THEORETICAL INVESTIGATIONS

UR - http://www.scopus.com/inward/record.url?scp=85044170606&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/halides-held-bifurcated-chalcogenhydrogen-bonds-effect-%CE%BCsnhcl-contacts-dimerization-clcarbenepdiispe

U2 - 10.1021/acs.inorgchem.8b00190

DO - 10.1021/acs.inorgchem.8b00190

M3 - Article

C2 - 29488765

VL - 57

SP - 3420

EP - 3433

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 6

ER -