Reactions of CO<sub>2</sub> and CS<sub>2</sub> with
[RuH(η<sup>2</sup>‑CH<sub>2</sub>PMe<sub>2</sub>)(PMe<sub>3</sub>)<sub>3</sub>]
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Abstract
Carbon disulfide reacted with the cyclometalated ruthenium
complex
[RuH(η<sup>2</sup>-CH<sub>2</sub>PMe<sub>2</sub>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>1</b>) at low temperature to yield the dithioformate
complex [Ru(η<sup>1</sup>-SC(S)H)(η<sup>2</sup>-CH<sub>2</sub>PMe<sub>2</sub>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>4</b>), where the CS<sub>2</sub> inserts into the metal hydride
bond. On warming, complex <b>4</b> rearranges to give the known
complex [Ru(S<sub>2</sub>CHPMe<sub>2</sub>CH<sub>2</sub>-κ<sup>3</sup><i>S</i>,<i>S</i>,<i>C</i>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>3</b>), where the CS<sub>2</sub> is
inserted in a metal phosphorus bond. Further reaction of this complex
with excess CS<sub>2</sub> over a period of days resulted in insertion
of a second CS<sub>2</sub> unit into one Ru–S bond to yield
[Ru(SC(S)SCH(-S)PMe<sub>2</sub>CH<sub>2</sub>-κ<sup>3</sup><i>S</i>,<i>S</i>,<i>C</i>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>5</b>). Complex <b>5</b> was
characterized crystallographically and by multinuclear NMR spectroscopy.
In contrast, reaction of [RuH(η<sup>2</sup>-CH<sub>2</sub>PMe<sub>2</sub>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>1</b>) with CO<sub>2</sub> resulted in insertion of CO<sub>2</sub> into the Ru–C
bond to give [RuH(OC(O)CH<sub>2</sub>PMe<sub>2</sub>-κ<sup>2</sup><i>O</i>,<i>P</i>)(PMe<sub>3</sub>)<sub>3</sub>] (<b>2</b>). Low-temperature NMR spectroscopic studies
did not show any evidence for prior formation of a formate complex
