TY - JOUR
T1 - Synthesis of conjugated diene complexes of ruthenium(0) derived from Ru(η 6-naphthalene)(η 4-1,5-COD)
T2 - Z to e isomerisation of coordinated 1,3-pentadiene
AU - Hirano, Masafumi
AU - Sakate, Yumiko
AU - Inoue, Haruka
AU - Arai, Yasutomo
AU - Komine, Nobuyuki
AU - Komiya, Sanshiro
AU - Wang, Xian Qi
AU - Bennett, Martin A.
PY - 2012/6/15
Y1 - 2012/6/15
N2 - The naphthalene complex of zerovalent ruthenium, [Ru(η 6- C 10H 8)(η 4-1,5-COD)] (1), readily reacts with 1,3-dienes in the presence of a ligand (L) to produce complexes [Ru(η 4-cisoid-1,3-diene)(η 4-1,5-COD)(L)] [1,3-diene = butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-cyclohexadiene; L = MeCN, tBuCN, PhCN, NCC 6H 4CN, CO, tBuNC, pyridine, P(OMe) 3, P(OPh) 3, PMe 3, PEt 3, PPh 3, PCy 3]. The single-crystal X-ray structures of [Ru(η 4-cisoid-1,3-butadiene)(η 4-1,5-COD)(MeCN)] (2a) and [Ru{η 4-(E)-cisoid-1.3-pentadiene}(η 4-1,5- COD)(PPh 3)}] (E-5l) show the expected, approximately square pyramidal geometry about the metal atom, with the auxiliary ligand occupying the axial site. [Ru{η 4-(Z)-cisoid-1,3-pentadiene}(η 4-1,5- COD)(PPh 3)] (Z-5l) irreversibly isomerises to E-5l in benzene-d 6 at 30 °C, the reaction obeying a first-order rate law [k = (2.89 ± 0.06) × 10 -4 s -1]. This reaction is significantly retarded by addition of PPh 3 suggesting that a vacant site is required for the E/Z isomerisation.
AB - The naphthalene complex of zerovalent ruthenium, [Ru(η 6- C 10H 8)(η 4-1,5-COD)] (1), readily reacts with 1,3-dienes in the presence of a ligand (L) to produce complexes [Ru(η 4-cisoid-1,3-diene)(η 4-1,5-COD)(L)] [1,3-diene = butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-cyclohexadiene; L = MeCN, tBuCN, PhCN, NCC 6H 4CN, CO, tBuNC, pyridine, P(OMe) 3, P(OPh) 3, PMe 3, PEt 3, PPh 3, PCy 3]. The single-crystal X-ray structures of [Ru(η 4-cisoid-1,3-butadiene)(η 4-1,5-COD)(MeCN)] (2a) and [Ru{η 4-(E)-cisoid-1.3-pentadiene}(η 4-1,5- COD)(PPh 3)}] (E-5l) show the expected, approximately square pyramidal geometry about the metal atom, with the auxiliary ligand occupying the axial site. [Ru{η 4-(Z)-cisoid-1,3-pentadiene}(η 4-1,5- COD)(PPh 3)] (Z-5l) irreversibly isomerises to E-5l in benzene-d 6 at 30 °C, the reaction obeying a first-order rate law [k = (2.89 ± 0.06) × 10 -4 s -1]. This reaction is significantly retarded by addition of PPh 3 suggesting that a vacant site is required for the E/Z isomerisation.
KW - 1,3-Pentadiene
KW - Conjugated diene
KW - E/Z isomerisation
KW - Ruthenium(0)
UR - http://www.scopus.com/inward/record.url?scp=84862777728&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2012.02.018
DO - 10.1016/j.jorganchem.2012.02.018
M3 - Article
SN - 0022-328X
VL - 708-709
SP - 46
EP - 57
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -