Research output: Contribution to journal › Article › peer-review
Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ-H)2Os3(CO)10]. / Afonin, M. Yu; Savkov, B. Yu; Virovets, A. V. et al.
In: European Journal of Inorganic Chemistry, Vol. 2017, No. 24, 30.06.2017, p. 3105-3114.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Transformation of Chlorohydrocarbons and Amines in the Coordination Sphere of [(µ-H)2Os3(CO)10]
AU - Afonin, M. Yu
AU - Savkov, B. Yu
AU - Virovets, A. V.
AU - Korenev, V. S.
AU - Golovin, A. V.
AU - Maksakov, V. A.
PY - 2017/6/30
Y1 - 2017/6/30
N2 - 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)2Os3(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 SN2 mechanism by SN2Hal.
AB - 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)2Os3(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 SN2 mechanism by SN2Hal.
KW - Amines
KW - Carbonyl complexes
KW - Cluster compounds
KW - C–H activation
KW - Halides
KW - Osmium
KW - ORGANOMETALLIC COMPOUNDS
KW - CARBENE LIGANDS
KW - CRYSTAL-STRUCTURE
KW - TERTIARY-AMINES
KW - TRIOSMIUM CLUSTERS
KW - X-RAY-STRUCTURE
KW - METAL-CARBONYL ANIONS
KW - H BOND ACTIVATION
KW - C-H activation
KW - CLUSTER COMPLEXES
KW - OXIDATIVE-ADDITION
UR - http://www.scopus.com/inward/record.url?scp=85021405488&partnerID=8YFLogxK
U2 - 10.1002/ejic.201700411
DO - 10.1002/ejic.201700411
M3 - Article
AN - SCOPUS:85021405488
VL - 2017
SP - 3105
EP - 3114
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
SN - 1434-1948
IS - 24
ER -
ID: 10096652