Structure of a scandium–carboxylate complex: (η5-C5Me5)2Sc(O2C)C6H4CH3

Reactivity of Yttrium Carboxylates Toward Alkylaluminum Hydrides

“…Overall, the two η 5 ‐coordinated Cp* rings and the carboxylate oxygen atoms form a pseudo‐tetrahedral coordination environment around the yttrium metal center in compound 1 , with YCp*(Ct) (Ct=centroid) distances that are similar to those found in [Cp* 2 Y(AlMe 4 )] (2.344/2.38 Å),11 but slightly shorter than those in [Cp* 2 Y{N(SiMe 3 ) 2 }] (2.391/2.400 Å),9 as well as a Cp*(Ct)‐Y‐Cp*(Ct) angle that is similar to that in [Cp* 2 Y(AlMe 4 )] (138.9°),11 but wider than in [Cp* 2 Y{N(SiMe 3 ) 2 }] (132.4°) 9. Similar yttriumoxygen distances (2.328(2)/2.315(2) Å) nicely display the symmetric η 2 ‐coordination of the benzoate ligand, which has also been observed in other monomeric carboxylate complexes, such as [Cp* 2 Sc(O 2 CC 6 H 4 ‐ p Me)]13 (2.167(3)/2.176(3) Å), and in dimeric complex [{Cp 2 Y(O 2 C(CH 2 ) 3 NMe 2 )} 2 ]16 (2.42(2)/2.40(2) Å, Cp=C 5 H 5 ). Another interesting feature is the tilt of the aromatic ring along the C1C2 bond relative to the CO 2 moiety, which is much more pronounced in compound 1 (35.8(3)°) than in [Cp* 2 Sc(O 2 CC 6 H 4 ‐ p Me)] (8.3(8)°) 16…”

“…X‐ray diffraction analysis revealed that compound 1 is a monomeric complex, in which the benzoate moiety is coordinated in a chelating fashion, as shown in Figure 1. Interestingly, only three other examples of monomeric cyclopentadienyl‐based lanthanide carboxylates have been reported, namely [(C 5 Me 4 t Bu) 2 Lu(O 2 CMe)],12 [Cp* 2 Sc(O 2 CC 6 H 4 ‐ p Me)],13 and [Cp* 2 Sm(O 2 CC 5 Me 5 )];14 other examples of lanthanide carboxylates are either dimers or even higher agglomerates 15. Overall, the two η 5 ‐coordinated Cp* rings and the carboxylate oxygen atoms form a pseudo‐tetrahedral coordination environment around the yttrium metal center in compound 1 , with YCp*(Ct) (Ct=centroid) distances that are similar to those found in [Cp* 2 Y(AlMe 4 )] (2.344/2.38 Å),11 but slightly shorter than those in [Cp* 2 Y{N(SiMe 3 ) 2 }] (2.391/2.400 Å),9 as well as a Cp*(Ct)‐Y‐Cp*(Ct) angle that is similar to that in [Cp* 2 Y(AlMe 4 )] (138.9°),11 but wider than in [Cp* 2 Y{N(SiMe 3 ) 2 }] (132.4°) 9.…”

CO2 Insertion Chemistry as a Probe of Organosamarium Allyl Reactivity

“…Organosamarium carboxylates can also be obtained from the related carboxylic acids by reduction with the divalent (C 5 Me 5 ) 2 Sm(THF) 2 . The direct reduction of benzoic and terephthalic acid by (C 5 Me 5 ) 2 Sm(THF) 2 to generate 10 and 11 in good yield provides an alternative general route for the preparation of metallocene lanthanide carboxylates, which have usually been prepared by metathesis or insertion of CO 2 . ,, Since a wider variety of carboxylic acids are available than well-characterized (C 5 Me 5 ) 2 SmR complexes, this is a broadly applicable route to organosamarium carboxylate products.…”

“…This study showed that CO 2 had some advantages in organolanthanide chemistry over the common insertion reagent CO , In contrast, CO 2 insertion is well-known in transition metal chemistry with examples involving metal allyl , as well as a variety of other metal ligand bonds …”

Crystal Structure of Lanthanide‐oxalate‐pyridine‐2,4‐dicarboxylate Coordination Polymers Suggesting the Reductive Coupling of Carbon Dioxide to Oxalate

“…chemical reductions of CO 2 to oxalate that give structurally well-characterized metal-oxalate compound. [22][23][24][25][26][27][28] We have performed some reactions to gain the mechanism for the formation of the oxalate. When we carried out the reactions in the present of sodium oxalate (Na 2 C 2 O 4 ) in the mole ratio of 1.00, 0.667 and 0.667 for Nd or Pr, 2,4-pydcH 2 and Na 2 C 2 O 4 , respectively, do not result in polymer 1 or 2.…”