%0 Generic
%A Fang, Ming
%A Farnaby, Joy H.
%A Ziller, Joseph W.
%A Bates, Jefferson
E.
%A Furche, Filipp
%A Evans, William J.
%D 2016
%T Isolation of (CO)1– and (CO2)1– Radical
Complexes of Rare Earths via
Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ Oligomerization
%U 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
%R 10.1021/ja211220r.s008
%2 https://acs.figshare.com/ndownloader/files/4174813
%K solvated variant
%K 2N
%K THF forms
%K OC
%K diethyl ether
%K CO 2
%K 1. Analogous
%K Rare Earths
%K CO reduction
%K reaction conditions
%X Deep-blue solutions of Y2+ formed from Y(NR2)3 (R = SiMe3) 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)1– radical complex, {[(R2N)3Y(μ-CO)2][K2(18-crown-6)2]}n, 1. The polymeric structure
contains trigonal bipyramidal [(R2N)3Y(μ-CO)2]2– units with axial (CO)1– ligands linked by [K2(18-crown-6)2]2+ dications. Byproducts such as the ynediolate, [(R2N)3Y]2(μ-OCCO){[K(18-crown-6)]2(18-crown-6)}, 2, in which two (CO)1– anions are coupled to form (OCCO)2–, and
the insertion/rearrangement product, {(R2N)2Y[OC(CH2)Si(Me2)NSiMe3]}[K(18-crown-6)], 3, 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 2, the
ynediolate [(R2N)3Y]2(μ-OCCO)[K(18-crown-6)(THF)2]2, 2a. CO2 reacts analogously
with Y2+ to form the (CO2)1– radical complex, {[(R2N)3Y(μ-CO2)2][K2(18-crown-6)2]}n, 4, that has a structure similar
to that of 1. Analogous (CO)1– and
(OCCO)2– complexes of lutetium were isolated
using Lu(NR2)3/K/18-crown-6: {[(R2N)3Lu(μ-CO)2][K2(18-crown-6)2]}n, 5, [(R2N)3Lu]2(μ-OCCO){[K(18-crown-6)]2(18-crown-6)}, 6, and [(R2N)3Lu]2(μ-OCCO)[K(18-crown-6)(Et2O)2]2, 6a.
%I ACS Publications