ISSN:
1042-7163
Keywords:
Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of 10-P-5 hydridophosphorane 6 with KH provides the 10-P-4 potassium phosphoranide anion 7a. Anion 7a reacts with CpFe(CO)2I and BrAu(PEt3) to replace the halide with the phosphoranide as a monodentate ligand forming 8 and 9. The X-ray structure of 8 shows that the equatorial - Fe(CO)2Cp ligand of 8 makes the apical P—O bonds (1.824 Å) longer than the P—O bonds (1.80 Å) of the phosphoranide oxide anion 10. The P—O bonds (1.75 Å) of 6, with an equatorial proton ligand, are still shorter. This provides evidence that the - Fe(CO)2Cp ligand is not only a sigma-acceptor Lewis acid ligand, but also a pi-donor that transfers electrons into the O—P—O three-center bond's anti-bonding orbital to increase its P - O bond lengths. It is a better pi-donor than the —O- pi-donor of phosphoranide oxide 10.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hc.520020110
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