ISSN:
0009-2940
Keywords:
Tetraaza-diphospha-stanna-bicycloheptanes
;
Tetraaza-tetraphospha-bicyclooctanes
;
1,3,2,4-Diazadiphosphetidines
;
1,3,2,4-Diazadistannetidines
;
SnN bond cleavage
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Tetraaza-λ31-diphospha-stanna-bicyclo[3.1.1]heptanes: Reactive Precursors of New Heterobicycles2,4,6,7-Tetraaza-1λ3,5λ31-diphospha-3-stannabicyclo[3.1.1]heptane (4) is obtained by stannazane cleavage of the diazadistannetidine (Me2SnNtBu)2 (2) with the diazadiphosphetidine (CIPNtBu)2 (1). A chloro derivative of 4, compound 8, is formed by substitution of one methyl group attached to the tin atom in 4 against chlorine in a 1:1 reaction with PhBCl2, while additional PhBCl2 leads to an exchange of the MeClSn against the PhB group to give 9. Oxidation of both phosphorus atoms of compound 4 with sulfur leads to 7. An unexpected introduction of a diphenyldiphosphane unit with formation of 11 proceeds by stannazane cleavage of 4 with PhPCl2. The structures of the bicyclic products 4, 7, 8, and 11 are ascertained by detailed NMR studies, particularly by means of 15N-NMR spectra, and by X-ray structure determinations. All heterobicycles contain a planar diazadiphosphetidine unit. The ring system 8 features an additional Sn - N bond due to transannular interaction of the tin atom with one of the nitrogen atoms of the four-membered P2N2 ring fragment. The PP bond distance in 11 with 2.175 Å is one of the shortest found in heterocycles containing P2 units.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260312
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