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Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H) 2 Os 3 (CO) 10 ]
Author(s) -
Afonin M. Yu.,
Savkov B. Yu.,
Virovets A. V.,
Korenev V. S.,
Golovin A. V.,
Maksakov V. A.
Publication year - 2017
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201700411
Subject(s) - chemistry , deprotonation , halogen , molecule , medicinal chemistry , coordination sphere , dichloromethane , bromine , amine gas treating , nucleophilic substitution , nucleophile , halocarbon , bond cleavage , chloride , coordination complex , ion , stereochemistry , metal , catalysis , organic chemistry , solvent , alkyl
A reaction has been found and investigated that demonstrates the potential for coordination, activation, and transformation of three organic molecules, namely, two dichloromethane molecules and one amine molecule, in the coordination sphere of the [(µ‐H)Os 3 (CO) 10 ] – carbonylate anion, which is formed in situ from the deprotonation of [(µ‐H) 2 Os 3 (CO) 10 ]. This reaction is very intricate and comprises such steps as the nucleophilic substitution of chloride ions by cluster carbonylate anions in the halocarbons, C–H, C–N, and C–Cl bond cleavage, and C–C and C–N bond formation under unusually mild conditions for such reactions leading to the formation of the CH=CH 2 ‐ or CH=CHNR 2 ‐bearing complexes [(µ‐Cl)Os 3 (µ 2 ‐σ,π‐CH=CH 2 )(CO) 10 ] and [(µ‐H)Os 3 (µ‐CH=CHNR 2 )(CO) 10 ]. The reaction is sensitive to the nature of the halogen in the halocarbon. When bromine or iodine was used in place of chlorine in the halohydrocarbons, [(µ‐H)Os 3 (µ‐X)(CO) 10 ] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the S N 2 mechanism by S N 2Hal.