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REACTIVITY OF TRIBORANE WITH PHOSPHINO PALLADIUM (II) AND PLATINUM (II) CHLORIDES
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Bilal A.M. SHAYKH
|
Univ. |
Cambridge |
Spec. |
Chemistry |
Deg. |
Year |
#Pages |
|
Ph.D. |
1990 |
245 |
This work reports the reactivity of palladium (II) and platinum (II) chloride complexes towards the octahydrotriborate (1-) anion. The bonding of the triborane fragment to the metal centre in pallada‑ and platinatetraborane complexes (PdB3 H7 and PtB3 H7) is different than in other metallatetraboranes (MB3 H8). A brief survey of the previously reported metellatetraboranes including their synthetic routes and spectroscopic properties is the subject of the introductory chapter.
The second and third chapters report the reactivity of complexes of the type (L‑L)PdCl2 and (L‑L)PtCl2 with [Me4 N] (B3 H8] where (L‑L) is either 1,1’‑bis (diphenylphosphino) ferrocene or α, ω -bis (diphenylphosphino) alkane ligand with alkane chains varying from methane to hexane. The reaction products and their relative yields were found to depend on both the metal centre and the phosphine ligand used. The generation of metallatetraborane complexes was noted for a number of reactions while the production of other complexes was noted in other cases. The role of the octahydrotriborate (1‑) anion as a hydride donor was established for a number of platinum (II) complexes. The fourth chapter reports the reactivity of the complex 1,2‑bis(diphenylphosphino) ethanepalladium heptahydrotetraborane with a variety of nucleophiles. The labilisation of the triborane fragment from the palladium (II) centre resulted in a failure to Isolate substituted palladatetraborane complexes. Dehydroboration of pallada‑ and platinatetraborane complexes was achieved by the use of 1,8‑diazabicyclo[5.4.0] unde‑7‑ene.
The fifth chapter reports the reactivity of palladium (II) and platinum (II) complexes containing triphosphine ligands towards the octathydrotriborate (I‑) anion. Two types of triphosphine ligands were used and the reactivity of their palladium (II) and platinum (II) chloride complexes towards (Me4 N) (B3 H8)was found to vary with the ligand and the metal centre used. In addition to the metallatetraborane complexes produced, the role of the octahydrotriborate (1‑) anion as a mild reducing agent to palladium (II) complexes and as a hydride donor to platinum (II) complexes was noted.
The concluding chapter sums up the results of previous chapters and gives suggestions for future work where some preliminary results which form the basis of these future plans are presented.
