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 -