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- Title
Metallacyclobuta‐(2,3)‐diene: A Bidentate Ligand for Stream‐line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene.
- Authors
Russell, John B.; Konar, Debabrata; Keller, Taylor M.; Gau, Michael R.; Carroll, Patrick J.; Telser, Joshua; Lester, Daniel W.; Veige, Adam S.; Sumerlin, Brent S.; Mindiola, Daniel J.
- Abstract
Described here is a direct entry to two examples of 3d transition metal catalysts that are active for the cyclic polymerization of phenylacetylene, namely, [(BDI)M{κ2‐C,C‐(Me3SiC3SiMe3)}] (2‐M) (BDI=[ArNC(CH3)]2CH−, Ar=2,6‐iPr2C6H3; M=Ti, V). Catalysts are prepared in one step by the treatment of [(BDI)MCl2] (1‐M, M=Ti, V) with 1,3‐dilithioallene [Li2(Me3SiC3SiMe3)]. Complexes 2‐M have been spectroscopically and structurally characterized and the polymers that are catalytically formed from phenylacetylene were verified to have a cyclic topology based on a combination of size‐exclusion chromatography (SEC) and intrinsic viscosity studies. Two‐electron oxidation of 2‐V with nitrous oxide (N2O) cleanly yields a [VV] alkylidene‐alkynyl oxo complex [(BDI)V(=O){κ1‐C‐(=C(SiMe3)CC(SiMe3))}] (3), which lends support for how this scaffold in 2‐M might be operating in the polymerization of the terminal alkyne. This work demonstrates how alkylidynes can be circumvented using 1,3‐dianionic allene as a segue into M−C multiple bonds.
- Subjects
TRANSITION metal catalysts; ETHYNYL benzene; INTRINSIC viscosity; POLYMERS; POLYMERIZATION; NITROUS oxide
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 8, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202318956