TY - JOUR
T1 - Geometric isomerization and geometry controlled catalytic alcohol aminations of ruthenium hydride compounds containing bidentate pyrrolyl-imines
AU - Li, Yong Jie
AU - Lai, Hsuan Ting
AU - Hu, Ching Han
AU - Chen, Jie Hong
AU - Lin, Chia Her
AU - Huang, Jui Hsien
PY - 2019/12/1
Y1 - 2019/12/1
N2 - A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.
AB - A series of ruthenium hydride compounds containing bidentate pyrrole-imine ligands were synthesized and characterized and their properties were fully studied. Reacting [C4H3NH-(2-CH=N-R) (L1H, R = CH2-2-furanyl; L2H, R = CH2-morpholine; L3H, R = CH2-2-pyridyl) with one equivalent of n-BuLi afforded the corresponding lithium reagents (LiL1∼LiL3). Combining RuHCl(CO)(PPh3)2 with LiL1∼LiL3 in THF at 0 °C with stirring at room temperature for 12 h generated pure trans-Pyr-Ru-H 1–3 in moderate yields after repeated fractional recrystallization. When the reactions were performed at reflux temperature, pure cis-Pyr-Ru-H 1–3 were obtained by fractional recrystallization in relatively high yields. A thermal isomerization study showed that pure cis-Pyr-Ru-H 1–3 and trans-Pyr-Ru-H 1–3 can be interconverted in THF after refluxing and equilibrium was attained. Reacting a bulkier ligand [C4H3NLi-(2-CH=N-tBu)] (LiL4) with one equivalent RuHCl(CO)(PPh3)3 at room temperature afforded only cis-Pyr-Ru-H 4 after purification. No trans-Pyr-Ru-H 4 was observed, indicating the bulkier t-butyl group of the L4 ligand altered the stability of cis- and trans-Pyr-Ru-H 4. A catalytic alcohol amination study showed the cis forms of Pyr-Ru-H were the active catalysts for converting benzyl alcohol to N-benzylaniline.
UR - http://www.scopus.com/inward/record.url?scp=85073162762&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85073162762&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2019.120957
DO - 10.1016/j.jorganchem.2019.120957
M3 - Article
AN - SCOPUS:85073162762
VL - 902
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
M1 - 120957
ER -