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Issue 19, 2016
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The chemistry of parent phosphiranide in the coordination sphere of tungsten

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Abstract

2-Chloroethylphosphine W(CO)5 complex 1 readily reacts with sodium hydride. With one equivalent of NaH, the parent phosphirane complex 3 is obtained. With more than two equivalents, the phosphiranide complex 2 is exclusively formed. With 1.5 equivalents, a 1 : 1 mixture of 2 and 3 is obtained but 2 readily attacks 3 at the phosphorus atom by splitting of ethylene and by the formation of the P–P complex 4. In turn, the P–P bond of 4 is split by NaH to yield the phosphide complex 8. The phosphiranide complex 2 is a good source for a large variety of functional phosphirane complexes 9. With BrCN, the 1-cyanophosphirane complex 9a is formed. Upon heating it loses its complexing group. Upon hydrolysis, it gives the 1-hydroxyphosphirane complex 12 which dimerizes in basic medium by opening one P–C bond of the ring to give 13. The reaction of 2 with PhPCl2 yields the triphosphorus complex 9g whose molecular structure has been established by X-ray crystal structure analysis.

Graphical abstract: The chemistry of parent phosphiranide in the coordination sphere of tungsten

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Article information


Submitted
11 Mar 2016
Accepted
07 Apr 2016
First published
12 Apr 2016

Dalton Trans., 2016,45, 8284-8290
Article type
Paper

The chemistry of parent phosphiranide in the coordination sphere of tungsten

Y. Hao, C. Zhang, Y. Mei, R. Tian, Z. Duan and F. Mathey, Dalton Trans., 2016, 45, 8284
DOI: 10.1039/C6DT00964F

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