ISSN:
0009-2940
Keywords:
Phosphaalkynes
;
Phosphinidenes
;
Phosphinidene Complexes
;
Cocyclooligomerization
;
Cage compounds, phosphorus-carbon
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Phosphaalkynes 2 undergo cocyclooligomerization reactions with the phosphinidene 14 or the phosphinidene-W(CO)5 complex 18 to furnish the phosphorus-carbon cage compounds 16 or 23. The phosphinidene 14 is generated by the thermal reaction of 2a-c with the phosphole 11, a process in which the initially formed 7-phosphanorbornadienes 12a-c decompose to the λ3-phosphinines 13a-c and the desired reactive intermediate. When three further equivalents of the phosphaalkynes 2a-c are employed, the tetraphosphahomoquadricyclanes 16a-c can be isolated in 53-65% yields. The second approach is based on the thermal fragmentation of 17 to generate the phosphinidene-W(CO)5 complex 18 which, in turn, reacts with four equivalents of the phosphaalkynes 2a or b to produce the pentaphosphadeltacyclanes 23a or b. The constitutions of these novel phosphorus-carbon cage compounds were confirmed by X-ray crystal structure analyses of 16a and 23a.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951281006
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