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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, J
The 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

Organometallics

Volume

30

Issue

6

Pagination

1569-1576

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

American Chemical Society

Place of publication

Washington, USA

Rights statement

Copyright Statement: Copyright © 2011 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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