Palladium Carbene Cluster: Synthesis, Structure and Reactivity
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Journal of Organometallic Chemistry
ISSN: 0022-328X
|
| Вых. Данные |
Год: 1991,
Том: 417,
Номер: 1-2,
Страницы: 193-204
Страниц
: 12
DOI:
10.1016/0022-328X(91)80173-H
|
| Ключевые слова |
COMPLEXES; LIGANDS |
| Авторы |
Stromnova Tatyana A.
1
,
Busygina Irina N.
1
,
Kochubey Dmitry I.
2
,
Moiseev Ilya I.
1
|
| Организации |
| 1 |
N.S. Kurnakov Institute of General and Inorganic Chemistry of the Academy of Sciences of the USSR, 31 Leninski Prosp., 117907 Moscow (USSR)
|
| 2 |
Institute of Catalysis, Siberian Branch of the Academy of Sciences of the USSR, Pr. akademika Lavrenteva 15, 630090 Novosibirsk (USSR)
|
|
The first palladium carbene cluster, μ-tetrakis(diphenylmethyliden)-μ-tetraacetato-quadro-tetrapalladium (4Pd-Pd) Pd4(μ-CPh2)4(μ-OAC)4 (I), has been synthesized by substitution of diphenylcarbene ligands for CO-groups in μ-tetrakis(carbonyl)-μ-tetraacetato-quadro-tetrapalladium (4Pd-Pd) Pd4(μ-CO)4(μ-OAc)4 (II) and characterized with EXAFS data. Reactivity of I, II and related clusters is discussed. Thermolysis of the clusters has been found to involve inner-sphere oxidation of carbene or carbonyl ligands during which an oxygen atom is transferred from the carboxylate group to the carbene or carbonyl ligand. Thermolysis of carbonyl clusters in benzene or toluene solutions gives rise to the products of CO2 insertion into the C-H bond of the solvent forming benzoic acid from benzene and a mixture of phenylacetic and tolyl acids from toluene.