Chlorine Oxidation of Coordinated Ethylenediamine
in Triamineplatinum(IV) Complex [PtEnPyCl₃]Cl.
Molecular Structure of [PtPy(NH₂CH₂CN)Cl₄]
and [PtPy(NCl(CH₂)₂NH₂)Cl₃] Crystals

I. B. Baranovskii, M. D. Surazhskaya, G. G. Aleksandrov, and M. A. Golubnichaya

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 119991 Russia

Received December 17, 2007

Abstract—The reaction of chlorine with triamine [PtEnPyCl₃]Cl in aqueous solution yields an insoluble pow-
dered product, which is a mixture of compounds. Extraction with acetonitrile isolates a number of complexes:
a glassy polymeric product (I), which contains a C=O group, an amino group, and pyridine;
[PtPy(NH₂CH₂CN)Cl₄] (II) as the major product (ethylenediamine converts to aminoacetonitrile as a result of
oxidative dehydrogenation); and the aminochloro complex [PtPy(NClCH₂CH₂NH₂)Cl₃] (III) in a minor
amount. The IR spectra of the products were studied. X-ray structure analysis was carried out for complexes II
and III. Compound II: orthorhombic space group Pbcm, a = 10.925(2) Å, b = 11.413(2) Å, c = 9.979(2) Å,
V=1244.3(4) ų, Z = 8, R_hk1 = 0.033. The aminoacetonitrile molecule is coordinated to the platinum atom via the
amino nitrogen atom in the trans position to pyridine; CN 1.07(2) Å, angle CCN 178(1). Compound III:
space group P2₁/n, a = 7.3016(8) Å, b = 7.8879(9) Å, c = 22.336(2) Å, = 96.107(2)°, V = 1279.1(2) ų, Z =4,
R_hk1 = 0.0808, N–Cl = 1.77(2) Å.

DOI: 10.1134/S0036023608070139

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