Cage-Structured Triplatinacyclophanes
Christian, H; Gerhard, B; Dieter, F
| HERO ID | 857954 |
|---|---|
| In Press | No |
| Year | 1999 |
| Title | Cage-Structured Triplatinacyclophanes |
| Authors | Christian, H; Gerhard, B; Dieter, F |
| Journal | European Journal of Inorganic Chemistry |
| Volume | 1999 |
| Page Numbers | 679 |
| Abstract | The synthesis of the tris(triflate) <B>4</B> (Scheme 1) has been achieved by means of a straightforward three-step reaction sequence. After initial lithiation of mesitylene, treatment of the obtained trilithium compound C<INF>6</INF>H<INF>3</INF>(CH<INF>2</INF>Li)<INF>3</INF> (<B>2</B>) with oxirane results in the formation of 1,3,5-tris(3-hydroxypropyl)benzene (<B>3</B>), which is then transformed to <B>4</B> by reaction with (CF<INF>3</INF>SO<INF>2</INF>)<INF>2</INF>O in the presence of pyridine. Whereas <B>4</B> reacts with Na<INF>2</INF>[Os(CO)<INF>4</INF>] in a somewhat complicated manner, similar reactions with Na[Re(CO)<INF>5</INF>] and LiPPh<INF>2</INF> give the hydrocarbon-bridged tris(rhenium) complex C<INF>6</INF>H<INF>3</INF>[(CH<INF>2</INF>)<INF>3</INF>Re(CO)<INF>5</INF>]<INF>3</INF> (<B>5</B>) and the tris(phosphane) C<INF>6</INF>H<INF>3</INF>[(CH<INF>2</INF>)<INF>3</INF>PPh<INF>2</INF>]<INF>3</INF> (<B>6</B>), respectively. Employing the high-dilution method, from <B>6</B> and Cl<INF>2</INF>Pt(NCPh)<INF>2</INF> the nanoscaled tri- and hexaplatinacyclophanes <B>7</B> and <B>9</B> are available. Owing to the optimal geometry and flexibility of the cage in <B>7</B>, 1,2-dichloroethane can be reversibly encapsulated. The molecular structure of <B>7</B> 7 1,2-Cl<INF>2</INF>C<INF>2</INF>H<INF>4</INF> was determined by an X-ray structure analysis. The utility of the reactive metal centers in <B>7</B> has been demonstrated by replacing the chloro ligands by acetonitrile to give the cationic platinacyclophane <B>8</B>, in which, according to NMR studies, the cage-like structure is preserved. |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Is Qa | No |