Diacetylplatinum(II) complexes [Pt(COMe)
2(N^N)] (N^N = bpy,
3a; 4,4′-
t-Bu
2-bpy,
3b) were found to undergo oxidative addition reactions with organyl halides. The reaction of
3a with methyl iodide and propargyl bromide led to the formation of the
cis addition products (
OC-6-34)-[Pt(COMe)
2(R)X(bpy)] (R = Me, X = I,
4a; CH
2C≡CH, X = Br,
4k). Analogous reactions of
3a with ethyl iodide, benzyl bromide, and substituted benzyl bromides, 3-(bromomethyl)pyridine, 2-(bromomethyl)thiophene, allyl
bromide, and cyclohex-2-enyl bromide led to exclusive formation of the
trans addition products (
OC-6-43)-[Pt(COMe)
2(R)X(bpy)] (X = I, R = Et,
4b; X = Br, R = CH
2C
6H
5,
4c; CH
2C
6H
4(
o-Br),
4d; CH
2C
6H
4(
p-COOH),
4e; CH
2-3-py (3-pyridylmethyl),
4f; CH
2-2-tp (2-thiophenylmethyl),
4g; CH
2CH=CH
2,
4h;
c-hex-2-enyl (cyclohex-2-enyl),
4i). All complexes
4 were characterized by microanalysis,
1H and
13C NMR and IR spectroscopy. Additionally, complexes
4a,
4f, and
4g were characterized by single-crystal X-ray diffraction analyses. Reactions of
3a and
3b with
o-,
m- and
p-bis(bromomethyl)benzene, respectively, led to the formation of dinuclear platinum(IV) complexes [{Pt(COMe)
2Br(N^N)}
2-{μ-(CH
2)
2C
6H
4}] (
5). These complexes were characterized by microanalysis, IR spectroscopy, and depending on their solubility by
1H and
13C NMR spectroscopy, too. A single-crystal X-ray diffraction analysis of complex [{Pt(COMe)
2Br(bpy)}
2{μ-
m-(CH
2)
2C
6H
4}] (
5b) confirmed its dinuclear composition. The solid-state structures of
4a,
4f,
4g, and
5b are discussed in terms of C–H···O and O–H···O hydrogen bonds as well as π–π stacking between aromatic rings.