✍ Scribed by M. Stumme; W. Preetz
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Professor Heinrich Vahrenkamp zum 60. Geburtstag gewidmet Inhaltsu È bersicht. An Einkristallen von (Ph 3 PNPPh 3 ) 2 [OsO 2 -(NCO) 4 ] (1) (orthorhombisch, Raumgruppe Pbca, a = 19,278(3), b = 16,674(4), c = 19,982(2) A Ê , Z = 4), trans-(n-Bu 4 N) 2 [OsO 2 (NCS) 4 ] (2) (triklin, Raumgruppe P1, a = 12,728(3), b = 12,953(3), c = 16,255(6) A Ê , a = 97,39(4), b = 105,62(2), c = 95,25(3)°, Z = 2) und trans-(n-Bu 4 N) 2 -[OsO 2 (SeCN) 4 ] (3) (tetragonal, Raumgruppe I4/m, a = 13,406(2), c = 12,871(1) A Ê , Z = 2) sind Ro È ntgenstrukturuntersuchungen durchgefu È hrt worden, die zeigen, daû NCO und NCS u È ber das N-Atom, SeCN aber u È ber das Se-Atom an Osmium koordiniert ist. Unter Verwendung der ro È ntgenographisch ermittelten Moleku È lparameter lassen sich die Schwingungsspektren durch Normalkoordinatenanalyse zuordnen. Die Valenzkraftkonstanten betragen fu È r 1 f d (OsO) = 6,43, f d (OsN) = 3,32, f d (NC) = 14,50, f d (CO) = 12,80, fu È r 2 f d (OsO) = 6,56, f d (OsN) = 1,75, f d (NC) = 15,00, f d (CS) = 5,50 und fu È r 3 f d (OsO) = 6,75, f d (OsSe) = 0,99, f d (SeC) = 3,23, f d (CN) = 15,95 mdyn/A Ê . Aus den NMR-Spektren ergeben sich die chemischen Verschiebungen d( 15 N) = ±386,6 (1), d( 15 N) = ±294,7 (2) und d( 77 Se) = 108,8 ppm (3). Crystal Structures, Normal Coordinate Analyses, and 15 N NMR and 77 Se NMR Chemical Shifts of trans-[OsO 2 (NCO) 4 ] 2± , trans-[OsO 2 (NCS) 4 ] 2± , and trans-[OsO 2 (SeCN) 4 ] 2± Abstract. The crystal structures of trans-(Ph 3 PNPPh 3 ) 2 -[OsO 2 (NCO) 4 ] (1) (orthorhombic, space group Pbca, a = 19.278(3), b = 16.674(4), c = 19.982(2) A Ê , Z = 4), trans-(n-Bu 4 N) 2 [OsO 2 (NCS) 4 ] (2) (triclinic, space group P1, a = 12.728(3), b = 12.953(3), c = 16.255(6) A Ê , a = 97.39(4), b = 105.62(2), c = 95.25(3)°, Z = 2) and trans-(n-Bu 4 N) 2 -[OsO 2 (SeCN) 4 ] (3) (tetragonal, space group I4/m, a = 13.406(2), c = 12.871(1) A Ê , Z = 2) have been determined by single-crystal X-ray diffraction analysis, showing the bonding of NCO and NCS via the N atom but the coordination of SeCN via the Se atom to osmium. Based on the molecular parameters of the X-ray determinations the vibra-tional spectra have been assigned by normal coordinate analyses. The valence force constants are for 1 f d (OsO) = 6.43, f d (OsN) = 3.32, f d (NC) = 14.50, f d (CO) = 12.80, for 2 f d (OsO) = 6.56, f d (OsN) = 1.75, f d (NC) = 15.00, f d (CS) = 5.50, and for 3 f d (OsO) = 6.75, f d (OsSe) = 0.99, f d (SeC) = 3.23, f d (CN) = 15.95 mdyn/A Ê . The observed NMR shifts are d( 15 N) = ±386.6 (1), d( 15 N) = ±294.7 (2) and d( 77 Se) = 108.8 ppm (3).
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