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Thermal isomerization of ruthenium hydride compounds containing asymmetric bidentate pyrrole‐imine ligands
Author(s) -
Lai HsuanTing,
Chen KunHao,
Li YongJie,
Wu ChengHsien,
Hu ChingHan,
Lin ChiaHer,
Huang JuiHsien
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201900156
Subject(s) - chemistry , hydride , isomerization , ruthenium , denticity , medicinal chemistry , imine , octahedron , stereochemistry , cis–trans isomerism , pyrrole , crystal structure , crystallography , catalysis , metal , organic chemistry
A series of ruthenium hydride compounds containing substituted bidentate pyrrole‐imine ligands were synthesized and characterized. Reacting RuHCl(CO)(PPh 3 ) 3 with one equivalent of [C 4 H 3 NH(2‐CH=NR)] in ethanol in the presence of KOH gave compounds {RuH(CO)(PPh 3 ) 2 [C 4 H 3 N(2‐CH=NR)]} where trans ‐Py‐Ru‐H 1, R = CH 2 CH 2 C 6 H 9 ; cis ‐Py‐Ru‐H 2, R = Ph‐2‐Me; and cis ‐Py‐Ru‐H 3, R = C 6 H 11 . Heating trans ‐Py‐Ru‐H 1 in toluene at 70°C for 12 hr resulted a thermal conversion of the trans ‐Py‐Ru‐H 1 into its cis form, {RuH(CO)(PPh 3 ) 2 [C 4 H 3 N(2‐CH=NCH 2 CH 2 C 6 H 9 )]} ( cis ‐Py‐Ru‐H 1) in very high yield. The 1 H NMR spectra of trans ‐Py‐Ru‐H 1, cis ‐Py‐Ru‐H 2, cis ‐Py‐Ru‐H 3, and cis ‐Py‐Ru‐H 1 all show a typical triplet at ca. δ–11 for the hydride. The trans and cis form indicate the relative positions of pyrrole ring and hydride. The geometries of trans ‐Py‐Ru‐H 1, cis ‐Py‐Ru‐H 1, and cis ‐Py‐Ru‐H 3 are relatively similar showing typical octahedral geometries with two PPh 3 fragments arranged in trans positions.