TY - JOUR
T1 - Rh(I)(2,5-norbornadiene)(biphenyl)(tris(4-fluorophenyl)phosphine)
T2 - Synthesis, Characterization, and Application as an Initiator in the Stereoregular (Co)Polymerization of Phenylacetylenes
AU - Loong Tan, Nicholas Sheng
AU - Nealon, Gareth L.
AU - Turner, Gemma F.
AU - Moggach, Stephen A.
AU - Ogden, Mark I.
AU - Massi, Massimiliano
AU - Lowe, Andrew B.
PY - 2020/1/21
Y1 - 2020/1/21
N2 - The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography.
AB - The synthesis of the Rh(I)-aryl complex, Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) is reported and its efficacy as an initiator for the (co)polymerization of phenylacetylenes established. The X-ray crystal structure indicates that the complex adopts a slightly distorted square planar geometry whose purity and structure was also confirmed by elemental analysis and 1H, 13C, 31P, 19F, 103Rh, and 31P-103Rh{1H} HMQC NMR spectroscopy. We demonstrate that Rh(I)(nbd)(BiPh)(P(4-FC6H4)3) mediates the (co)polymerization of phenylacetylenes in a controlled fashion with initiation efficiencies as high as 0.98, as evidenced by the pseudo-first-order kinetic and number-average molecular weight versus conversion profiles. The ability to form well-defined AB diblock copolymers, in a stereoregular manner, by sequential monomer addition is verified in the block copolymerization of phenylacetylene with 4-fluorophenylacetylene with quantitative crossover efficiency, as determined by size exclusion chromatography.
UR - http://www.scopus.com/inward/record.url?scp=85077442511&partnerID=8YFLogxK
U2 - 10.1021/acsmacrolett.9b00975
DO - 10.1021/acsmacrolett.9b00975
M3 - Article
AN - SCOPUS:85077442511
SN - 2161-1653
VL - 9
SP - 56
EP - 60
JO - ACS Macro Letters
JF - ACS Macro Letters
IS - 1
ER -