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Rhodium(I)‐α‐Phenylvinylfluorenyl Complexes: Synthesis, Characterization, and Evaluation as Initiators in the Stereospecific Polymerization of Phenylacetylene
Author(s) -
Tan Nicholas Sheng Loong,
Simpson Peter V.,
Nealon Gareth L.,
Sobolev Alexandre N.,
Raiteri Paolo,
Massi Massimiliano,
Ogden Mark I.,
Lowe Andrew B.
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801411
Subject(s) - phenylacetylene , chemistry , rhodium , norbornadiene , heteronuclear molecule , polymerization , phosphine , diphosphines , nuclear magnetic resonance spectroscopy , polymer chemistry , stereochemistry , crystallography , organic chemistry , catalysis , polymer
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‐FC 6 H 4 ) 3 , Rh(nbd)(CPh=CFlu)P(4‐CF 3 C 6 H 4 ) 3 , and Rh(nbd)(CPh=CFlu)P[3,5‐(CF 3 ) 2 C 6 H 3 ] 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 1 H, 31 P, 19 F, 103 Rh NMR spectroscopy and 2D 31 P‐ 103 Rh/ 31 P‐ 103 Rh{ 103 Rh} 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 = M w / M n ) with high cis‐transoidal stereoregularity.