Eleven-Vertex Polyhedral Dicarbaplatinaborane Chemistry. Aspects of the Chemistry of Some closo-Structured {1,2,3-PtC2B8} Species and Some Related Compounds

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Title:Eleven-Vertex Polyhedral Dicarbaplatinaborane Chemistry. Aspects of the Chemistry of Some closo-Structured {1,2,3-PtC2B8} Species and Some Related Compounds
Creators:
Kennedy, John D.
Štíbr, Bohumil
Jelínek, Tomáš
Fontaine, Xavier L. R.
Thornton-Pett, Mark
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 58, 9, pp. 2090-2120

Abstract

The reaction of the ten-vertex <i>nido</i> anions [6,9-C<sub>2</sub>B<sub>8</sub>H<sub>10</sub>]<sup>2-</sup>, [6-Me-6,9-C<sub>2</sub>B<sub>8</sub>H<sub>9</sub>]<sup>2-</sup> and [6-Ph-6,9-C<sub>2</sub>B<sub>8</sub>H<sub>9</sub>]<sup>2-</sup> with [<i>cis</i>-PtCl<sub>2</sub>(PMe<sub>2</sub>Ph)<sub>2</sub>] in CH<sub>2</sub>Cl<sub>2</sub> yields the yellow crystalline <i>closo</i>-structured eleven-vertex compounds [2-X-1,1-(PMe<sub>2</sub>Ph)<sub>2</sub>-1,2,3-PtC<sub>2</sub>B<sub>8</sub>H<sub>9</sub>], where X = H (compound 1), Me (compound 2), or Ph (compound 3) in yields of 58 88%. These compounds have been characterized by multielement NMR spectroscopy and, in the case of compounds 1 and 2, by single-crystal X-ray diffraction analysis. Crystals of compound 1 were monoclinic, space group <i>P</i>2<sub>1</sub>/<i>n</i>, with <i>a</i> = 947.6(1), <i>b</i> = 1 547.7(3), <i>c</i> = 1 804.0(3) pm, β = 104.78(1)°, and <i>Z</i> = 4, solved and refined to <i>R</i> (<i>R</i><sub>w</sub>) = 0.0216 (0.0234) with 4 200 unique reflections <i>I</i> &gt; 2.0 σ(<i>I</i>). Crystals of compound 2 were monoclinic, space group <i>I</i>2/<i>a</i> (= <i>C</i>2/<i>c</i>), with <i>a</i> = 1 824.8(2), <i>b</i> = 1 016.8(2), <i>c</i> = 1 328.2(3) pm, β = 101.48(2)°, and <i>Z</i> = 4, solved and refined to <i>R</i> (<i>R</i><sub>w</sub>) = 0.0442 (0.0474) with 2 057 unique reflections <i>I</i> &gt; 2.0 σ(<i>I</i>). The NMR and X-ray results reveal that the closed eleven-vertex compounds [2-X-1,1-(PR<sub>3</sub>)<sub>2</sub>-1,2,3-PtC<sub>2</sub>B<sub>8</sub>H<sub>9</sub>] exhibit a previously unsuspected but very free contrarotational fluxionality within the constrains of their η<sup>6</sup>-carborane-to-metal bonding that is accompanied by a marked flexing of the η<sup>6</sup>-{C<sub>2</sub>B<sub>8</sub>H<sub>9</sub>X} moiety between <i>nido</i> and <i>arachno</i> ten-vertex geometries and electronic characteristics. The structural and bonding implications are discussed and elucidated specifically with reference to the NMR and geometrical charcteristics of [<i>closo</i>-2,3- C<sub>2</sub>B<sub>9</sub>H<sub>11</sub>], [<i>arachno</i>-6,9- C<sub>2</sub>B<sub>8</sub>H<sub>14</sub>] and the [<i>nido</i>-6-X-6,9- C<sub>2</sub>B<sub>8</sub>H<sub>9</sub>]<sup>2-</sup> anions, together with other pertinent species such as [μ-6,9-(SnMe<sub>2</sub>)-<i>nido</i>-6,9-C<sub>2</sub>B<sub>8</sub>H<sub>10</sub>] and more generally with reference to other eleven-vertex metallaheteroborano species. The general behaviour patterns thus established are summarized.

Title:Eleven-Vertex Polyhedral Dicarbaplatinaborane Chemistry. Aspects of the Chemistry of Some closo-Structured {1,2,3-PtC2B8} Species and Some Related Compounds
Creators:
Kennedy, John D.
Štíbr, Bohumil
Jelínek, Tomáš
Fontaine, Xavier L. R.
Thornton-Pett, Mark
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:58
Number:9
Page Range:pp. 2090-2120
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19932090UNSPECIFIED
ID Code:331
Item Type:Article
Deposited On:06 Feb 2009 17:00
Last Modified:06 Feb 2009 16:00

Citation

Kennedy, John D.; Štíbr, Bohumil; Jelínek, Tomáš; Fontaine, Xavier L. R.; Thornton-Pett, Mark (1993) Eleven-Vertex Polyhedral Dicarbaplatinaborane Chemistry. Aspects of the Chemistry of Some closo-Structured {1,2,3-PtC2B8} Species and Some Related Compounds. Collection of Czechoslovak Chemical Communications, 58 (9). pp. 2090-2120. ISSN 0010-0765

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