10.1021/ic500866d.s002
Jing Huang
Jing
Huang
Jinzhu Chen
Jinzhu
Chen
Hui Gao
Hui
Gao
Limin Chen
Limin
Chen
Kinetic Aspects for the Reduction of CO<sub>2</sub> and CS<sub>2</sub> with Mixed-Ligand Ruthenium(II) Hydride Complexes
Containing Phosphine and Bipyridine
American Chemical Society
2014
Ru
CS 2 insertion reaction
PTA
CO 2
CS 2 insertion
k 2
CO 2 insertion reaction
1 b
CS 2. 1 b
methanol
CS 2
1000 times
CO 2 insertion
2014-09-15 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Kinetic_Aspects_for_the_Reduction_of_CO_sub_2_sub_and_CS_sub_2_sub_with_Mixed_Ligand_Ruthenium_II_Hydride_Complexes_Containing_Phosphine_and_Bipyridine/2254948
A new
water-soluble ruthenium hydride complex [Ru(H)(bpy)<sub>2</sub>(PTA)]PF<sub>6</sub> (bpy = 2,2′-bipyridine, PTA = 1,3,5-triaza-7-phosphaadamantane)
(<b>1a</b>) was prepared. <b>1a</b> reacted with CO<sub>2</sub> and CS<sub>2</sub> to give the corresponding formate and
dithioformate complexes, respectively. Both the insertions of CO<sub>2</sub> and CS<sub>2</sub> into the Ru–H bond of <b>1a</b> followed second-order kinetics. The second-order rate constant (<i>k</i><sub>2</sub>) of CO<sub>2</sub> insertion reaction varied
from (9.40 ± 0.41) × 10<sup>–4</sup> M<sup>–1</sup> s<sup>–1</sup> in acetone to (1.13 ± 0.08) × 10<sup>–1</sup> M<sup>–1</sup> s<sup>–1</sup> in methanol;
moreover, the ln(<i>k</i><sub>2</sub>) is in good linear
relationship with the acceptor number (AN) of the solvent used. Although,
the <i>k</i><sub>2</sub> of CS<sub>2</sub> insertion reaction
ranged from (3.43 ± 0.10) M<sup>–1</sup> s<sup>–1</sup> in methanol to (24.0 ± 0.5) M<sup>–1</sup> s<sup>–1</sup> in <i>N</i>,<i>N</i>-dimethylformamide, which
is 1000 times faster than CO<sub>2</sub> insertion. Generally, the <i>k</i><sub>2</sub> of CS<sub>2</sub> insertion increased with
the static dielectric constant (<i>D</i><sub>s</sub>) of
the reaction medium investigated. For comparison purposes, we further
investigated the reactivity of [Ru(H)(bpy)<sub>2</sub>(PPh<sub>3</sub>)]PF<sub>6</sub> (PPh<sub>3</sub> = triphenylphosphine) (<b>1b</b>) with CO<sub>2</sub> and CS<sub>2</sub>. <b>1b</b> reacted
with CO<sub>2</sub> slowly in the methanol with a <i>k</i><sub>2</sub> of (1.46 ± 0.09) × 10<sup>–3</sup> M<sup>–1</sup> s<sup>–1</sup>, yielding a formate complex
[Ru(η<sup>1</sup>-OC(H)O)(bpy)<sub>2</sub>(PPh<sub>3</sub>)]PF<sub>6</sub> (<b>2b</b>). The reaction of <b>1b</b> with CS<sub>2</sub> is 1000 times faster than that of CO<sub>2</sub>. The structures of <b>1a</b>, <b>1b</b>, and <b>2b</b> were determined by X-ray crystallographic analysis.