New Class of Ruthenium Sulfide Clusters: Ru<sub>4</sub>S<sub>6</sub>(PPh<sub>3</sub>)<sub>4</sub>, Ru<sub>5</sub>S<sub>6</sub>(PPh<sub>3</sub>)<sub>5</sub>,\nand Ru<sub>6</sub>S<sub>8</sub>(PPh<sub>3</sub>)<sub>6</sub>
Amanda L. Eckermann (1597717)Markus Wunder (2278189)Dieter Fenske (2275519)Thomas B. Rauchfuss (1308867)Scott R. Wilson (2190925)
Abstract
Reaction of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with S<sup>2-</sup> sources yields a family of\nphosphine-containing Ru−S clusters which have been characterized\ncrystallographically and by MALDI-MS. Ru<sub>4</sub>S<sub>6</sub>(PPh<sub>3</sub>)<sub>4</sub> (Ru−Ru<sub>av</sub> =\n2.94 Å) has idealized <i>T</i><i><sub>d</sub></i> symmetry whereas Ru<sub>6</sub>S<sub>8</sub>(PPh<sub>3</sub>)<sub>6</sub> (Ru−Ru<sub>av</sub> = 2.82 Å) adopts the idealized <i>O</i><i><sub>h</sub></i> symmetry characteristic\nof Chevrel clusters. Ru<sub>5</sub>S<sub>6</sub>(PPh<sub>3</sub>)<sub>5</sub> is formally derived by the addition\nof Ru(PPh<sub>3</sub>) to one face of Ru<sub>4</sub>S<sub>6</sub>(PPh<sub>3</sub>)<sub>4</sub>. In terms of its M−S\nconnectivity, the Ru<sub>5</sub>S<sub>6</sub> cluster resembles a fragment of the FeMo\ncluster in nitrogenase.
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