10.1021/ja211220r.s008
Ming Fang
Ming
Fang
Joy H. Farnaby
Joy H.
Farnaby
Joseph W. Ziller
Joseph W.
Ziller
Jefferson
E. Bates
Jefferson
E.
Bates
Filipp Furche
Filipp
Furche
William J. Evans
William J.
Evans
Isolation of (CO)<sup>1–</sup> and (CO<sub>2</sub>)<sup>1–</sup> Radical
Complexes of Rare Earths via
Ln(NR<sub>2</sub>)<sub>3</sub>/K Reduction and [K<sub>2</sub>(18-crown-6)<sub>2</sub>]<sup>2+</sup> Oligomerization
American Chemical Society
2016
solvated variant
2N
THF forms
OC
diethyl ether
CO 2
1. Analogous
Rare Earths
CO reduction
reaction conditions
2016-02-21 14:51:33
Dataset
https://acs.figshare.com/articles/dataset/Isolation_of_CO_sup_1_sup_and_CO_sub_2_sub_sup_1_sup_Radical_Complexes_of_Rare_Earths_via_Ln_NR_sub_2_sub_sub_3_sub_K_Reduction_and_K_sub_2_sub_18_crown_6_sub_2_sub_sup_2_sup_Oligomerization/2531812
Deep-blue solutions of Y<sup>2+</sup> formed from Y(NR<sub>2</sub>)<sub>3</sub> (R = SiMe<sub>3</sub>) and excess potassium
in the
presence of 18-crown-6 at −45 °C under vacuum in diethyl
ether react with CO at −78 °C to form colorless crystals
of the (CO)<sup>1–</sup> radical complex, {[(R<sub>2</sub>N)<sub>3</sub>Y(μ-CO)<sub>2</sub>][K<sub>2</sub>(18-crown-6)<sub>2</sub>]}<sub><i>n</i></sub>, <b>1</b>. The polymeric structure
contains trigonal bipyramidal [(R<sub>2</sub>N)<sub>3</sub>Y(μ-CO)<sub>2</sub>]<sup>2–</sup> units with axial (CO)<sup>1–</sup> ligands linked by [K<sub>2</sub>(18-crown-6)<sub>2</sub>]<sup>2+</sup> dications. Byproducts such as the ynediolate, [(R<sub>2</sub>N)<sub>3</sub>Y]<sub>2</sub>(μ-OCCO){[K(18-crown-6)]<sub>2</sub>(18-crown-6)}, <b>2</b>, in which two (CO)<sup>1–</sup> anions are coupled to form (OCCO)<sup>2–</sup>, and
the insertion/rearrangement product, {(R<sub>2</sub>N)<sub>2</sub>Y[OC(CH<sub>2</sub>)Si(Me<sub>2</sub>)NSiMe<sub>3</sub>]}[K(18-crown-6)], <b>3</b>, are common in these reactions that give variable results
depending on the specific reaction conditions. The CO reduction in
the presence of THF forms a solvated variant of <b>2</b>, the
ynediolate [(R<sub>2</sub>N)<sub>3</sub>Y]<sub>2</sub>(μ-OCCO)[K(18-crown-6)(THF)<sub>2</sub>]<sub>2</sub>, <b>2a</b>. CO<sub>2</sub> reacts analogously
with Y<sup>2+</sup> to form the (CO<sub>2</sub>)<sup>1–</sup> radical complex, {[(R<sub>2</sub>N)<sub>3</sub>Y(μ-CO<sub>2</sub>)<sub>2</sub>][K<sub>2</sub>(18-crown-6)<sub>2</sub>]}<sub><i>n</i></sub>, <b>4</b>, that has a structure similar
to that of <b>1</b>. Analogous (CO)<sup>1–</sup> and
(OCCO)<sup>2–</sup> complexes of lutetium were isolated
using Lu(NR<sub>2</sub>)<sub>3</sub>/K/18-crown-6: {[(R<sub>2</sub>N)<sub>3</sub>Lu(μ-CO)<sub>2</sub>][K<sub>2</sub>(18-crown-6)<sub>2</sub>]}<sub><i>n</i></sub>, <b>5</b>, [(R<sub>2</sub>N)<sub>3</sub>Lu]<sub>2</sub>(μ-OCCO){[K(18-crown-6)]<sub>2</sub>(18-crown-6)}, <b>6</b>, and [(R<sub>2</sub>N)<sub>3</sub>Lu]<sub>2</sub>(μ-OCCO)[K(18-crown-6)(Et<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>, <b>6a</b>.