Abstract
This contribution reports on the insertion of CO2 into actinide methyl and hydride bonds to yield acetate and formate complexes, respectively. Thus, addition of excess CO2 to Cp′2MMe2 (Cp′ = η5- C5Me5, M = Th, U) results in the formation of Cp′2- M(OAc)2 complexes in high yield. These new complexes, which could also be prepared from Cp′2- MCl2 and 2 equiv. of NaOAc, were characterized by standard techniques. On the basis of infrared data and molecular weight measurements the bis(acetate) compounds are suggested to be monomeric with two bidentate acetate ligands, thus achieving a 10-coordinate geometry about the metal ion. The addition of only 1 equiv. of CO2 to Cp′2MMe2 yields Cp′2MMe(OAc) complexes exclusively, suggesting that the formation of the bis(acetate) complexes proceeds sequentially. These complexes could also be prepared via metathesis of the corresponding Cp′2MMeCl complexes with NaOAc. Although the reaction of CO2 with [Cp′2Th(μ-H)(H)]2 produces a variety of uncharacterizable products, Cp′2Th(O2CH)(OCH-t-Bu) was formed upon treatment of Cp′2Th(H)(OCH-t-Bu) with CO2.
| Original language | English |
|---|---|
| Pages (from-to) | 127-131 |
| Number of pages | 5 |
| Journal | Inorganica Chimica Acta |
| Volume | 110 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - 1985 |
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ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
The insertion of carbon dioxide into actinide alkyl and hydride bonds. / Moloy, Kenneth G.; Marks, Tobin J.
In: Inorganica Chimica Acta, Vol. 110, No. 2, 1985, p. 127-131.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - The insertion of carbon dioxide into actinide alkyl and hydride bonds
AU - Moloy, Kenneth G.
AU - Marks, Tobin J
PY - 1985
Y1 - 1985
N2 - This contribution reports on the insertion of CO2 into actinide methyl and hydride bonds to yield acetate and formate complexes, respectively. Thus, addition of excess CO2 to Cp′2MMe2 (Cp′ = η5- C5Me5, M = Th, U) results in the formation of Cp′2- M(OAc)2 complexes in high yield. These new complexes, which could also be prepared from Cp′2- MCl2 and 2 equiv. of NaOAc, were characterized by standard techniques. On the basis of infrared data and molecular weight measurements the bis(acetate) compounds are suggested to be monomeric with two bidentate acetate ligands, thus achieving a 10-coordinate geometry about the metal ion. The addition of only 1 equiv. of CO2 to Cp′2MMe2 yields Cp′2MMe(OAc) complexes exclusively, suggesting that the formation of the bis(acetate) complexes proceeds sequentially. These complexes could also be prepared via metathesis of the corresponding Cp′2MMeCl complexes with NaOAc. Although the reaction of CO2 with [Cp′2Th(μ-H)(H)]2 produces a variety of uncharacterizable products, Cp′2Th(O2CH)(OCH-t-Bu) was formed upon treatment of Cp′2Th(H)(OCH-t-Bu) with CO2.
AB - This contribution reports on the insertion of CO2 into actinide methyl and hydride bonds to yield acetate and formate complexes, respectively. Thus, addition of excess CO2 to Cp′2MMe2 (Cp′ = η5- C5Me5, M = Th, U) results in the formation of Cp′2- M(OAc)2 complexes in high yield. These new complexes, which could also be prepared from Cp′2- MCl2 and 2 equiv. of NaOAc, were characterized by standard techniques. On the basis of infrared data and molecular weight measurements the bis(acetate) compounds are suggested to be monomeric with two bidentate acetate ligands, thus achieving a 10-coordinate geometry about the metal ion. The addition of only 1 equiv. of CO2 to Cp′2MMe2 yields Cp′2MMe(OAc) complexes exclusively, suggesting that the formation of the bis(acetate) complexes proceeds sequentially. These complexes could also be prepared via metathesis of the corresponding Cp′2MMeCl complexes with NaOAc. Although the reaction of CO2 with [Cp′2Th(μ-H)(H)]2 produces a variety of uncharacterizable products, Cp′2Th(O2CH)(OCH-t-Bu) was formed upon treatment of Cp′2Th(H)(OCH-t-Bu) with CO2.
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U2 - 10.1016/S0020-1693(00)84568-5
DO - 10.1016/S0020-1693(00)84568-5
M3 - Article
VL - 110
SP - 127
EP - 131
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 2
ER -