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Revisiting the Aufbau Reaction with Acetylene: Further Insights from Experiment and Theory


Karpiniec, SS and McGuinness, DS and Gardiner, MG and Yates, BF and Patel, J, Revisiting the Aufbau Reaction with Acetylene: Further Insights from Experiment and Theory, Organometallics, 30, (6) pp. 1569-1576 . ISSN 0276-7333 (2011) [Refereed Article]

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Copyright Statement

Copyright Statement: Copyright 2011 American Chemical Society

DOI: doi:10.1021/om101114c


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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Main group metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Karpiniec, SS (Mr Samuel Karpiniec)
UTAS Author:McGuinness, DS (Dr David McGuinness)
UTAS Author:Gardiner, MG (Associate Professor Michael Gardiner)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:72175
Year Published:2011
Web of Science® Times Cited:8
Deposited By:Chemistry
Deposited On:2011-08-23
Last Modified:2012-05-10
Downloads:1 View Download Statistics

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