ISSN:
0044-2313
Keywords:
Phosphoraneiminato Complexes of Iodine
;
Synthesis
;
Crystal Structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Phosphoraneiminato Complexes of Iodine. Syntheses and Crystal Structures of Ph3PNIO2 and Ph3PNSiMe3 · I2Ph3PNIO2 has been prepared as yellow crystals by the reaction of Ph3PNSiMe3 with I2O5 in boiling acetonitrile, whereas the molecular complex Ph3PNSiMe3 · I2 is formed as brown crystals by the reaction of Ph3PNSiMe3 with iodine in acetonitrile solution. Both complexes were characterized by crystal structure determinations.Ph3PNIO2: Space group P21/n, Z = 4, 2 858 observed unique reflections, R = 0.039. Lattice dimensions at 19°C: a = 972.8(2), b = 1 743.4(3), c = 1 073.7(2) pm, β = 115.46(3)°. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9°) is unusually small; the PN bond length of 159.2 pm corresponds with a double bond.Ph3PNSiMe3 · I2: Space group P1, Z = 2, 3 560 observed unique reflections, R = 0.033. Lattice dimensions at 19°C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, α = 78.34(1)°, β = 72.00(2)°, γ = 86.08(2)°. The compound forms monomeric molecules, in which the I2 molecule and the nitrogen atom of the phosphoraneimine molecule realize a linear N—I—I axis with a bond length N—I of 243.2 pm.
Notes:
Ph3PNIO2 entsteht als gelbe Kristalle durch Reaktion von Ph3PNSiMe3 und I2O5 in siedendem Acetonitril, während der Molekülkomplex Ph3PNSiMe3 · I2 aus Ph3PNSiMe3 und Iod bei Raumtemperatur in Acetonitril in Form brauner Kristallnadeln gebildet wird. Beide Komplexe haben wir durch röntgenographische Strukturanalysen charakterisiert.Ph3PNIO2: Raumgruppe P21/n, Z = 4, 2858 beobachtete unabhängige Reflexe, R = 0,039. Gitterabmessungen bei 19°C: a = 972,8(2); b = 1 743,4(3); c = 1 073,7(2) pm, β = 115,46(3)°. Die Verbindung bildet monomere Moleküle mit pyramidaler Geometrie am Iodatom. Der Bindungswinkel PNI ist mit 126,9° ungewöhnlich klein; der Abstand PN entspricht mit 159,2 pm einer Doppelbindung.Ph3PNSiMe3 · I2: Raumgruppe P1, Z = 2, 3 560 beobachtete unabhängige Reflexe, R = 0,033. Gitterabmessungen bei 19°C: a = 941,2(2); b = 1 041,7(2); c = 1 287,4(3) pm; α = 78,34(1)°; β = 72,00(2)°; γ = 86,08(2)°. Die Verbindung bildet monomere Moleküle, in denen das I2-Molekül mit dem N-Atom des Phosphanimins eine lineare N—I—I-Achse mit einem N—I-Abstand von 243,2 pm realisiert.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19946200221
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