ISSN:
0009-2940
Keywords:
(9-Anthracenyl)phosphanes
;
photo-dimerization of
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The syntheses of the (9-anthracenyl)phosphanes 2 to 7 and of the metal carbonyl complexes 8 and 9 are described. Both 1 and 4 undergo [4 + 4] cycloaddition when irradiated, forming the dimers 10 and 11. Only one of the six possible rotamers for 10 is formed. For 11 one additional rotational isomer is observed. The relationship between the [4 + 4] dimerization and steric effects of the PR2 group is discussed. The compounds 6, 8 and 11 were characterized by X-ray diffraction. The structure of 6 was rendered imprecise by the presence of disordered toluene, but the influence of the bulky anthracenyl groups was clear, with wide C—P—C angles of 110.4°. The molecule displays imposed threefold symmetry. The two independent molecules of complex 8, which crystallizes as a dichloromethane hemisolvate, are closely similar to each other; the W—P bond lengths are 254.3 and 253.4 pm. The W—C bonds trans to phosphorus are 4 pm shorter than those cis. The phosphane dimer 11 crystallizes with imposed centrosymmetry. The H atom positions, which could be tentatively identified from difference syntheses, indicate a different rotamer than was formed for the analogous fluorophosphane dimer 10.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921251005
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