Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ‐H)2Os3(CO)10]. Issue 24 (29th June 2017)

• Record Type: Journal Article
• Authors: Afonin, M. Yu.; Savkov, B. Yu.; Virovets, A. V.; Korenev, V. S.; Golovin, A. V.; Maksakov, V. A.
• Is Part Of: European journal of inorganic chemistry. Issue 24(2017)
• Page Start: 3105
• Page End: 3114
• Publication Date: 2017-06-29
• Subjects: Osmium -- Cluster compounds -- C–H activation -- Carbonyl complexes -- Amines -- Halides; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700411
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : 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)Os3 (CO)10 ] – carbonylate anion, which is formed in situ from the deprotonation of [(µ‐H)2 Os3 (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=CH2 ‐ or CH=CHNR2 ‐bearing complexes [(µ‐Cl)Os3 (µ2 ‐σ, π‐CH=CH2 )(CO)10 ] and [(µ‐H)Os3 (µ‐CH=CHNR2 )(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)Os3 (µ‐X)(CO)10 ] (X = Br, I) clusters were obtained in good yields, which apparently indicates the replacement of the SN 2 mechanism by SN 2Hal. Abstract : Three organic molecules, two CH2 Cl2 and an amine, react in the coordination sphere of the [(µ‐H)Os3 (CO)10 ] – anion, formed in situ from the deprotonation of [(µ‐H)2 Os3 (CO)10 ], to give [(µ‐Cl)Os3 (µ2 ‐σ, π‐CH=CH2 )(CO)10 ] and [(µ‐H)Os3 (µ‐CH=CHNR2 )(CO)10 ]. When CH2 Br2 or CH2 I2 was used in place of CH2 Cl2, [(µ‐H)Os3 (µ‐X)(CO)10 ] (X = Br, I) clusters were obtained in good yields by a different mechanism.