Stereoselective Alkyne Insertion into a Bridging Hydride at a Diiron Centre: cis-trans Isomerisation and Metallacycle Formation

DOI: 10.1039/DT9940003389

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3389 - 3396 (1994)

Update date:2022-08-02

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Authors:

Hogarth, Graeme

Lavender, Mark H.

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Article abstract of DOI:10.1039/DT9940003389

Addition of the activated alkyne dimethyl acetylenedicarboxylate (dmad) to 1 (dppm = Ph2PCH2PPh2) afforded the ?-η vinyl complex cis-(μ-PPh2)(μ-dppm)> 2.Crystallography showed that the insertion is stereoselectively cis, with the phosphorus-containing ligands also adopting a cis configuration.Ultraviolet irradiation of 2 resulted in slow conversion into a second isomer, trans-(μ-PPh2)(μ-dppm)> 3, which still retains the cis arrangement of phosphines as shown by 31P NMR spectroscopy.This transformation is reversible, 3 slowly converting back into 2 at room temperature, a process which is accelerated upon heating.At temperatures of >/= 80 deg C, 2 (and 3) was converted irreversibly into a third isomer (μ-PPh2)(μ-dppm)> 4, containing a metallacyclic ring by virtue of metal co-ordination of an ester carbonyl.X-Ray crystallography revealed a trans vinyl orientation and a trans disposition of the phosphorus-containing groups.

Full text of DOI:10.1039/DT9940003389

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