title: Direct observation of deuterium migration in crystalline-state reaction by single crystal neutron diffraction IV. "Hula-twist" rotation of a long alkyl radical produced by photoirradiation.
abstract: When the crystal of [(R)-1,2-bis(ethoxycarbonyl)ethyl](pyridine)bis(dimethylglyoximato)cobalt(III) was exposed to a xenon lamp, the chiral 1,2-bis(ethoxycarbonyl)ethyl group was partly inverted to the opposite configuration and finally the racemic group was produced with retention of the single crystal form. To make clear the mechanism, the hydrogen atom bonded to the chiral carbon of the chiral group was exchanged with the deuterium atom and the crystal was exposed to the xenon lamp for 3 days. The crystal after irradiation was analyzed by neutron diffraction. About 33% of the (R)-isomers were inverted to the (S) isomers in a crystal. The deuterium atom in the (S)-isomer was bonded to the same chiral carbon atom. This result clearly indicates that the inversion proceeds in the three steps; (i) the Co-C bond was homolytically cleaved by photoirradiation and the 1,2-bis(ethoxycarbonyl)ethyl radical and Co(II) were produced, (ii) the radical rotated by 180 degrees directing the C-D bond to the cobalt atom and the opposite plane of the radical faced to the cobalt atom, and (iii) the radical made a bond with Co(II). Because the peripheral atoms of the long radical occupy approximately the same positions in the process of the radical rotation, the crystal was not decomposed. The above rotation is a good example of hula-twist rotation in the process of photoisomerization of polyenes such as rhodopsin.
authors.affiliation: Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Oho, Tsukuba, Ibaraki 305-0801, Japan.
authors.forename: Takashi
authors.initials: T
authors.lastname: Ohhara
authors.forename: Susumu
authors.initials: S
authors.lastname: Ikeda
authors.forename: Hiroyuki
authors.initials: H
authors.lastname: Imura
authors.forename: Hidehiro
authors.initials: H
authors.lastname: Uekusa
authors.forename: Yuji
authors.initials: Y
authors.lastname: Ohashi
authors.forename: Ichiro
authors.initials: I
authors.lastname: Tanaka
authors.forename: Nobuo
authors.initials: N
authors.lastname: Niimura
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003903:Deuterium / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D033363:Neutron Diffraction; D009942:Organometallic Compounds / Q000737:chemistry*; D010777:Photochemistry; D014805:Vitamin B 12 / Q000737:chemistry
chemical_list: C470906:1,2-bis(ethoxycarbonyl)ethyl(pyridine)bis(dimethylglyoximato)cobalt(III); D009942:Organometallic Compounds; D003035:Cobalt; D003903:Deuterium; D014805:Vitamin B 12