Darstellung, 11B-NMR-, Schwingungsspektren und Kristallstruktur von (PPh4)[1-(NO)B10H9]

✍ Scribed by C. Nachtigal; W. Preetz

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: German
• Weight: 102 KB
• Volume: 624
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199802)624:2<327::aid-zaac327>3.0.co;2-8

✦ Synopsis

Inhaltsu È bersicht. Beim Einleiten von NO 2 in eine wa È ûrige Acetonitrillo È sung von (n-Bu 4 N) 2 [B 10 H 10 ] entsteht ein Produktgemisch, aus dem [1-(NO)B 10 H 9 ] ± durch Ionenaustauschchromatographie an Diethlylaminoethyl(DEAE)-Cellulose isoliert worden ist. Die Ro È ntgenstrukturanalyse an (PPh 4 )[1-(NO)B 10 H 9 ] (triklin, Raumgruppe P1, a = 7,6553(11), b = 13,179(2), c = 14,122(3) A Ê , α = 69,853(13), b = 82,445(14), c = 87,230(13)°, Z = 2) beweist die Bindung der NO-Gruppe u È ber das N-Atom in apikaler Position des B 10 -Clusters mit den Bindungsla È ngen B1±N = 1,457(5) und N±O = 1,101(4) A Ê . Im 11 B-NMR-Spektrum beobachtet man das charakteristische Signalmuster (1 : 1 : 4 : 4) eines in 1-Position substituierten B 10 -Clusters mit starkem Tieffeldshift des ipso-B-Kerns bei +6,5 ppm. Im IR-und Raman-Spektrum tritt eine intensive NO-Valenzschwingung bei 2219 cm ±1 auf. Synthesis, 11 B NMR, Vibrational Spectra, and Crystal Structure of (PPh 4 )[1-(NO)B 10 H 9 ] Abstract. By reaction of (n-Bu 4 N) 2 [B 10 H 10 ] in aqueous acetonitrile with NO 2 a reaction mixture is formed from which [1-(NO)B 10 H 9 ] ± has been isolated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose. The X-ray structure determination of (PPh 4 )[1-(NO)B 10 H 9 ] (triclinic, space group P1, a = 7.6553(11), b = 13.179(2), c = 14.122(3) A Ê , α = 69.853(13), b = 82.445(14), c = 87.230(13)°, Z = 2) reveals the coordination of the NO group via N in an apical position of the B 10 cluster with B1±N = 1.457(5) and N±O = 1.101(4) A Ê . The 11 B NMR spectrum exhibits the characteristic feature (1 : 1 : 4 : 4) of a in 1 position substituted B 10 cluster with a strong downfield shift of the ipso-B atom at +6.5 ppm. The IR and Raman spectra show a strong NO stretching vibration at 2219 cm ±1 .