(Isocyano Group π‐Hole)⋅⋅⋅[d‐MII] Interactions of (Isocyanide)[MII] Complexes, in which Positively Charged Metal Centers (d8‐M=Pt, Pd) Act as Nucleophiles

• DOI: 10.1002/chem.201901187
• Publication Date: 2019-04-12T15:47:51Z
• Authors: Svetlana A. Katkova; Alexander S. Mikh...; Mikhail A. Kinzhalov; Alexander S. Novikov; Andrey A. Zolotarev; Vadim P. Boyarskiy; Vadim Yu. Kukushkin
• Keywords: Acceptor; Atoms in molecules

Inspection of the X-ray structures newly prepared trans-[MII (CNXyl)2 (DAPT)2 ]Cl(BF4 ) (M=Pd, Pt; Xyl=2,6-Me2 C6 H3 ; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and appropriate Hirshfeld molecular surface analysis allowed recognition previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as π-hole donor) positively charged d8 -PtII -PdII metal centers nucleophiles); this is first identification with triple-bond species. Results DFT calculations followed by topological electron density distribution within framework Bader's theory (quantum atoms in molecules, QTAIM) confirmed presence these contacts. The electrostatic potential indicated that contacts are formed upon interaction electrophilic C atom (π-hole nucleophilic d z2 orbital centers, which act acceptors. Available CCDC data were processed from perspective isocyanide ligands, their disclosed role nucleophilicity corresponding acceptor ability.