High-nuclearity ruthenium carbonyl cluster chemistry. 9. Ligand substitution at decaruthenium carbonyl clusters

作者：Randles Michael D; Cifuentes Marie P; Moxey Graeme J; Zahl Achim; van Eldik Rudi; Humphrey Mark G^*

来源：Journal of Organometallic Chemistry, 2017, 849-850: 63-70.

DOI：10.1016/j.jorganchem.2017.05.026

• Ruthenium
• High-nuclearity clusters
• Kinetics
• X-ray structure

The mono-to tri-substituted decaruthenium cluster anions [Ru-10(mu-H)(mu(6)-C)(CO)(24-x)(L)(x)](-) [L = P(C6H4Me-4)(3), AsPh3, SbPh3, x = 1-3] were prepared as their [PPh4](+) salts in moderate to good yields from reaction of [PPh4][Ru-10(mu-H)(mu(6)-C)(CO)(24)] with the corresponding group 15 ligands at room temperature in acetone. The tetrakis-substituted cluster Ru-10(mu(6)-C)(mu(3)-CO)(mu-CO)(CO)(19){P(C6H4Me-4)(3)}(4) was obtained in high yield from [PPh4](2)[Ru-10(mu(6)-C)(CO)(24)] and an excess of the phosphine under the same conditions; a single-crystal X-ray diffraction study revealed that the phosphines ligate at the vertices of the "giant tetrahedral" core. Kinetics studies of the formation of [PPh4][Ru-10(mu-H)(mu(6)-C)(AsPh3)(2)(CO)(22)] from [PPh4][Ru-10(mu-H)(mu(6)-C)(AsPh3)(CO)(23)] shows that ligand substitution at these giant tetrahedral clusters proceeds via a strongly associative pathway with the likely intermediacy of a Ru-Ru bond-cleaved intermediate.

• 出版日期2017-11-1