TY - JOUR
T1 - Rhodium(I)-α-Phenylvinylfluorenyl Complexes
T2 - Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene
AU - Tan, Nicholas Sheng Loong
AU - Simpson, Peter V.
AU - Nealon, Gareth L.
AU - Sobolev, Alexandre N.
AU - Raiteri, Paolo
AU - Massi, Massimiliano
AU - Ogden, Mark I.
AU - Lowe, Andrew B.
PY - 2019/2/7
Y1 - 2019/2/7
N2 - The synthesis, characterization and use, as initiators for phenylacetylene polymerizations, of three new rhodium(I)-vinyl complexes containing fluorenyl functionality with fluorine-functionalized phosphine ligands is described. Rh(nbd)(CPh=CFlu)P(4-FC6H4)3, Rh(nbd)(CPh=CFlu)P(4-CF3C6H4)3, and Rh(nbd)(CPh=CFlu)P[3,5-(CF3)2C6H3]3 (nbd: 2,5-norbornadiene; Flu: fluorenyl) were prepared and isolated as discrete, orange compounds and were readily recrystallized yielding X-ray quality crystals. All complexes were characterized by a combination of 1H, 31P, 19F, 103Rh NMR spectroscopy and 2D 31P-103Rh/31P-103Rh{103Rh} heteronuclear multiple-quantum correlation (HMQC) experiments, elemental analysis, and single-crystal X-ray analysis. The complexes were active as initiators in the co-ordination insertion polymerization of phenylacetylene, with initiation efficiencies spanning the range 13–56 %, and yielded polyphenylacetylenes of low dispersity (Ð = Mw/Mn) with high cis-transoidal stereoregularity.
AB - The synthesis, characterization and use, as initiators for phenylacetylene polymerizations, of three new rhodium(I)-vinyl complexes containing fluorenyl functionality with fluorine-functionalized phosphine ligands is described. Rh(nbd)(CPh=CFlu)P(4-FC6H4)3, Rh(nbd)(CPh=CFlu)P(4-CF3C6H4)3, and Rh(nbd)(CPh=CFlu)P[3,5-(CF3)2C6H3]3 (nbd: 2,5-norbornadiene; Flu: fluorenyl) were prepared and isolated as discrete, orange compounds and were readily recrystallized yielding X-ray quality crystals. All complexes were characterized by a combination of 1H, 31P, 19F, 103Rh NMR spectroscopy and 2D 31P-103Rh/31P-103Rh{103Rh} heteronuclear multiple-quantum correlation (HMQC) experiments, elemental analysis, and single-crystal X-ray analysis. The complexes were active as initiators in the co-ordination insertion polymerization of phenylacetylene, with initiation efficiencies spanning the range 13–56 %, and yielded polyphenylacetylenes of low dispersity (Ð = Mw/Mn) with high cis-transoidal stereoregularity.
KW - Phenylacetylene
KW - Rhodium
KW - Stereospecific polymerization
UR - http://www.scopus.com/inward/record.url?scp=85059686107&partnerID=8YFLogxK
U2 - 10.1002/ejic.201801411
DO - 10.1002/ejic.201801411
M3 - Article
AN - SCOPUS:85059686107
SN - 1434-1948
VL - 2019
SP - 592
EP - 601
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 5
ER -