Journal article
Reactivity of diacetylplatinum(II) complexes: oxidative addition of alkyl halides and crystal structures of acetyl platinum(IV) complexes



Publication Details
Authors:
Bruhn, C.
Publication year:
2009
Journal:
Transition Metal Chemistry
Pages range:
61-74
Volume number:
34
Start page:
61
End page:
74
ISSN:
0340-4285

Abstract
Diacetylplatinum(II) complexes [Pt(COMe)(2)-(NN)] (NN=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; CH2C 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=CH2C6H5, 4c; CH2C6H4(o-Br), 4d; CH2C6H4(p-COOH), 4e; CH2-3-py (3-pyridylmethyl), 4f; CH2-2-tp (2-thiophenylmethyl), 4g; CH2CH=CH2, 4h; c-hex-2-enyl (cyclohex-2-enyl), 4i). All complexes 4 were characterized by microanalysis, H-1 and C-13 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)(2)Br(NN)}(2){mu-(CH2)(2)C6H4}] (5). These complexes were characterized by microanalysis, IR spectroscopy, and depending on their solubility by H-1 and C-13 NMR spectroscopy, too. A single-crystal X-ray diffraction analysis of complex [{Pt(COMe)(2)Br(bpy)} 2{mu-m(CH2)(2)C6H4}] (5b) confirmed its dinuclear composition. The solid-state structures of 4a, 4f, 4g, and 5b are discussed in terms of C-H center dot center dot center dot O and O-H center dot center dot center dot O hydrogen bonds as well as p - p stacking between aromatic rings.


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