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Revisiting the Aufbau Reaction with Acetylene: Further Insights from Experiment and Theory
journal contribution
posted on 2023-05-17, 07:24 authored by Karpiniec, SS, McGuinness, DS, Michael GardinerMichael Gardiner, Brian YatesBrian Yates, Patel, JThe first steps of acetylene chain growth at AlEt(3), via migratory insertion, have been investigated both experimentally and theoretically. The first insertion into the Al-Et bond occurs readily, leading to the stable alkenyl-bridged dimer [{Et(2)Al(mu-CH=CHEt)}(2)] (1). The alkenyl bridging mode has been observed through isolation and structural analysis of Al(2)Et(2)(OC(6)H(3)Ph(2))(2)(mu-CH=CHEt)(mu-OC(6)H(3)Ph(2)) (2), synthesized by way of controlled reaction of 1 with 2,6-Ph(2)C(6)H(3)OH. This stable binding mode increases the barrier to a second insertion of acetylene, as insertion proceeds through monomeric Al-acetylene adducts. The energetics of further chain growth, dimer formation, and chain termination via hydrogenolysis were investigated theoretically. The results provide further insight and explanation for previous experimental findings in relation to the Aufbau reaction with acetylene.
History
Publication title
OrganometallicsVolume
30Issue
6Pagination
1569-1576ISSN
0276-7333Department/School
School of Natural SciencesPublisher
American Chemical SocietyPlace of publication
Washington, USARights statement
Copyright Statement: Copyright © 2011 American Chemical SocietyRepository Status
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