TY - JOUR

T1 - Experimental and computational tuning of metalla-N-heterocyclic carbenes at palladium(ii) and platinum(ii) centers

AU - Kashina, Maria V.

AU - Luzyanin, Konstantin V.

AU - Katlenok, Eugene A.

AU - Novikov, Alexander S.

AU - Kinzhalov, Mikhail A.

N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry

PY - 2022/3/14

Y1 - 2022/3/14

N2 - Palladium(ii) and platinum(ii) complexes featuring metalla-N-heterocyclic carbenes (7-12) were synthesised via metal-mediated coupling between equimolar cis-[MCl2(CNR)2] (R = 2,6-Me2C6H3 (Xyl), 2,4,6-Me3C6H3 (Mes)) and 2-aminopyridine or 2-aminopyrazine. Thiocyanate complexes 13-18 with two thiocyanate ligands were obtained through the ligand exchange in the parent compounds 7-12 with NH4CNS in acetone/CH2Cl2. Complexes 7-18 were isolated and characterised by HRESI+-MS, IR, 1H and 13C{1H} NMR spectroscopy and single-crystal X-ray diffraction (in the case of 11, 16, and 18). The UV-vis properties of 7-18 and the electrochemical properties of 7-12 were also evaluated. To study the electronic structure and bonding nature in the new compounds, the quantum theory of atoms in molecules (QTAIM) and Mayer bond order analysis together with the extended transition state with the natural orbitals for chemical valence (ETS-NOCV) method, were used. X-ray diffraction studies and theoretical considerations indicate that the thiocyanate derivatives 16 and 18 form supramolecular dimers by two symmetrical pairs M1⋯C5 and S1⋯C2 with short intermolecular contacts between an electron-rich MII-center and thiocyanate ligand on the one side and the electron-poor π-system of an azaheterocyclic ring on the other side. Representative carbenes 8, 11 and 12 were evaluated as photocatalysts for the hydrosilylation of diphenylacetylene with triethylsilane giving 1,2-(diphenylvinyl)triethylsilane in 98% yield under visible light irradiation (blue light, 445 nm).

AB - Palladium(ii) and platinum(ii) complexes featuring metalla-N-heterocyclic carbenes (7-12) were synthesised via metal-mediated coupling between equimolar cis-[MCl2(CNR)2] (R = 2,6-Me2C6H3 (Xyl), 2,4,6-Me3C6H3 (Mes)) and 2-aminopyridine or 2-aminopyrazine. Thiocyanate complexes 13-18 with two thiocyanate ligands were obtained through the ligand exchange in the parent compounds 7-12 with NH4CNS in acetone/CH2Cl2. Complexes 7-18 were isolated and characterised by HRESI+-MS, IR, 1H and 13C{1H} NMR spectroscopy and single-crystal X-ray diffraction (in the case of 11, 16, and 18). The UV-vis properties of 7-18 and the electrochemical properties of 7-12 were also evaluated. To study the electronic structure and bonding nature in the new compounds, the quantum theory of atoms in molecules (QTAIM) and Mayer bond order analysis together with the extended transition state with the natural orbitals for chemical valence (ETS-NOCV) method, were used. X-ray diffraction studies and theoretical considerations indicate that the thiocyanate derivatives 16 and 18 form supramolecular dimers by two symmetrical pairs M1⋯C5 and S1⋯C2 with short intermolecular contacts between an electron-rich MII-center and thiocyanate ligand on the one side and the electron-poor π-system of an azaheterocyclic ring on the other side. Representative carbenes 8, 11 and 12 were evaluated as photocatalysts for the hydrosilylation of diphenylacetylene with triethylsilane giving 1,2-(diphenylvinyl)triethylsilane in 98% yield under visible light irradiation (blue light, 445 nm).

UR - http://www.scopus.com/inward/record.url?scp=85129537445&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/061c70da-78e8-3832-97a2-8c43bb66fdee/

U2 - 10.1039/d2dt00252c

DO - 10.1039/d2dt00252c

M3 - Article

C2 - 35415731

AN - SCOPUS:85129537445

VL - 51

SP - 6718

EP - 6734

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 17

ER -