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Reactivity of (C sub 5 Me sub 5 ) sub 2 SM with aryl-substituted alkenes: Synthesis and structure of a bimetallic styrene complex that contains an. eta. sup 2 -arene lanthanide interaction

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00157a035· OSTI ID:6660345
(C{sub 5}Me{sub 5}){sub 2}Sm (1) and (C{sub 5}Me{sub 5}){sub 2}Sm(THF){sub 2} (2) isomerize cis-stilbene to trans-stilbene. The stoichiometric reaction of 1 with stilbene forms ((C{sub 5}Me{sub 5}){sub 2}Sm){sub 2}({mu}-{eta}{sup 2}-{eta}{sup 4}-PhCHCHPh) (3). 1 reacts with styrene to form ((C{sub 5}Me{sub 5}){sub 2}Sm){sub 2}({mu}-{eta}{sup 2}-{eta}{sup 4}-CH{sub 2}CHPh) (4). In both 3 and 4, the two (C{sub 5}Me{sub 5}){sub 2}Sm units coordinate on opposite sides of the alkene bond such that the Sm-Sm vector bisects the bond at right angles. In each complex, phenyl carbon atoms are oriented to interact with one of the samarium centers. In 4, the Sm-C(C{sub 5}Me{sub 5}) distances range from 2.678 (18) to 2.847 (18) {angstrom}, the Sm-C(alkene) distances range from 2.537 (15) to 2.732 (15) {angstrom}, and two carbon atoms of the phenyl ring are positioned 2.772 (17) and 2.850 (16) {angstrom} from one samarium atom. 3 crystallizes from hexane in space group P2{sub 1}2{sub 1}2 with a = 12.156 (6) {angstrom}, b = 14.405 (9) {angstrom}, c = 15.628 (2) {angstrom}, and V = 2737 (2) {angstrom}{sup 3} with Z = 2 for D{sub calcd} = 1.24 g cm{sup {minus}3}. 4 crystallizes from hexane in space group Pbca with a = 21.169 (4) {angstrom}, b = 17.663 (3) {angstrom}, c = 23.713 (5) {angstrom}, and V = 8866 (3) {angstrom}{sup 3} with Z = 8 for D{sub calcd} = 1.417 g cm{sup {minus}3}. Least-squares refinement of the model based on 3134 observed reflections converged to a final R{sub F} = 6.2%.
OSTI ID:
6660345
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:1; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English