Study of Allylic Rearrangement in (μ-H)Os3(μ-O=CNRCH2CH=CH2)(CO) 10 (R = H or CH3) Clusters
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Translated
|
| Journal |
Russian Chemical Bulletin
ISSN: 1066-5285
, E-ISSN: 1573-9171
|
| Output data |
Year: 1999,
Volume: 48,
Number: 11,
Pages: 2158-2161
Pages count
: 4
DOI:
10.1007/BF02494867
|
| Tags |
1H, 2H, and 13C NMR spectroscopy, Allylic rearrangement, Catalysis, Isotopically labeled complexes, Triosmium clusters |
| Authors |
Maksakov V.A.
,
Kirin V.P.
,
Tkachev S.V.
,
Golovin A.V.
|
| Affiliations |
| 1 |
Nikolaev Institute of Inorganic Chemistry SB RAS
|
|
The migration of the double bond in the allylcarboxamide ligands of (μ-H)Os3(μ-O=CN RCH2CH=CH2) (CO)10 (R=H (1) or CH3 (2)), (μ-D)Os3(μ-O=CNDCH2CH=CH2) (CO)10, and (μ-H)Os3(μ-O=CNHCD2CH=CH2)(CO)10 clusters was studied by1H,2H, and13C NMR spectroscopy. Neither μ-D nor ND groups in the deuterated complexes are directly involved in prototropic processes of allylic rearrangement. Initially, the deuterium atom of the CD2 group migrates to the ψ-carbon atom of the allyl fragment to form the −CD=CH-CH2D propenyl moiety, in which the deuterium and hydrogen atoms are gradually redistributed between the ψ-and β-carbon atoms. The triosmium cluster complexes containing the bridging carboxamide ligands O=CNRR' catalyze the allylic rearrangement ofN-allylacetamide. Based on the data obtained, the probable scheme of the allylic rearrangements in clusters1 and2 was proposed.