124917-90-4Relevant academic research and scientific papers
The Reaction of 2-C(R)=CHR>(μ-PPh2)(CO)7> (R = H or Ph) with Nucleophiles: X-Ray Crystal Structures of (μ-PPh2)(CO)6>, (CO)9>, , μ-PPh2)(CO)6(CNBut)2>,
Henrick, Kim,McPartlin, Mary,Iggo, Jonathan A.,Kemball, Alan C.,Mays, Martin J.,Raithby, Paul R.
, p. 2669 - 2682 (2007/10/02)
The reaction of 2-C(R)=CHR>(μ-PPh2)(CO)7> (R = H or Ph) with the nucleophiles H-, CO, ButNC and PEt3 have been studied and the structures of six of the products of these reactions have been determined by X-ray diffraction.In all of the products the nucleophile is bound to the metal but the course of a given reaction is highly sensitive both to the nature of the nucleophile and to the substituents on the μ-vinyl group.With H- as the nucleophile and R = Ph the principal products is the μ-acyl complex (μ-PPh2)(CO06> in which the Mn-Mn distance of 2.813(1) Angstroem indicates the presence of a metal-metal bond.With CO as the nucleophile a P-C coupling reaction between the μ-PPh2 and the μ-vinyl ligand is induced (R = H or Ph) leading via (CO)8> to the final product (CO)9> which results from the addition of a second molecule of the nucleophile.The structures of both of these P-C linked complexes have been determined by X-ray diffraction, the former for R = H and the latter for R = Ph.The Mn-Mn separations for these two complexes are 2.957(1) and 2.941(1) Angstroem, respectively.With ButNC as the nucleophile and R = Ph a μ-acyl complex (μ-PPh2)(CO)6(CNBut)2>, is also obtained as the principal product but the X-ray diffraction study reveals an Mn-Mn separation of 3.820(2) Angstroem indicating the absence of a metal-metal iteraction.A second product obtained in this reaction has been shown by an X-ray diffraction study to be the ButNC-substituted vinyl derivative 2-C(Ph)=CHPh>(μ-PPh2)(CO)6(CNBut)> in which the Mn-Mn distance is 2.758(1) Angstroem.With phosphines as the nucleophiles, complex mixtures of products are, in general, obtained and these products have not all been characterised.With PEt3 and R = H, however, the principal products is the P-C linked complex and this has been isolated and structurally characterised by an X-ray diffraction study which shows that the Mn-Mn distance is 2.989(3) Angstroem.Finally, with ButNC as the nucleophile and R = H a compound is formed which is tentatively assigned a structure analogous to that obtained with PEt3 as the nucleophile.Some reaction pathways which account for the formation of the major products in the above reactions are proposed and discussed.
Transformations of a μ2-Vinyl Ligand at a Dimanganese Centre and the Flexibility of μ2-Acyl Ligands; X-Ray Crystal Structures of 2-H)2-C(O)CPh:CHPh>(μ2-PPh2)(CO)6>, 2-C(O)CPh:CHPh>(μ2-PPh2)(CO)6(CNBut)2>, and 3-P(Ph)2CH:CH2>(C...
Henrick, Kim,Iggo, Jonathan A.,Mays, Martin J.,Raithby, Paul R.
, p. 209 - 211 (2007/10/02)
2-?:η2-CR:CHR)(μ2-PPh2)(CO)7> (R = H or Ph) reacts with 2-electron donor ligands to give μ2-acyl complexes or products containing the P(Ph)2CR:CHR ligand; these correspond, respectively, to insertion of CO or PPh2 into the ?-bond between the metal and the μ2-vinyl group.
