Reaction of K2[PtCl4] with excess AlkSCN
in water gives the alkylthiocyanate complexes trans-[PtCl2(AlkSCN)2] (Alk = Et 1,
n
Pr 2; 80–85%).
These species were studied, in particular, by X-ray crystallography.
In the solid state, both 1 and 2 exhibit
the previously unreported S···Cl chalcogen bonding,
which consolidates the complexes into networks and leads to layered
structures. Theoretical density functional theory calculations and
Bader’s atoms in molecules analysis demonstrated two types
of intermolecular interactions in tetramer (1)4, viz. the S···Cl chalcogen and the H···Cl
hydrogen bonds. Despite that each particular S···Cl
or H···Cl bonding is weak with the estimated energy
of 1–2 kcal/mol, altogether they play a crucial role in the
stabilization of the S2Cl2 fragment in (1)4, the basis set of superposition error corrected
interaction energy being −12.8 kcal/mol per monomer complex
molecule. The chalcogen bonding and the rhomboidal structure of the
S2Cl2 fragment can be interpreted in terms of
electrostatic arguments as a result of the interaction between the
belt of negative electrostatic potential around the Cl atoms and the
sulfur σ-holes. The natural bond orbital analysis revealed that
both LP(S) → LP*(Pt)/σ*(Pt–N)/σ*(Pt–Cl)
and LP(Cl) → σ*(S–C) types of hyperconjugative
charge transfers are important in the chalcogen bonding.
Oxadiazole derivatives [(III) and (V)] are selectively synthesized through a one‐step route under mild conditions by Zn(II)‐activated reaction of N‐alkyl ketonitrones (I) with cyanamides (II).
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