All operations were carried out under nitrogen in anhydrous solvent. 3: 31P(1H) NMR (CD,CI,, 121.50MHz): 6 = -6.47 (s, PPh,); 13C( The reader of this article may assume a serious printing error in the formulation of the title compound as Ag,CeO,; it is correct, however, and the unusual composition of this NMR (CD,Cl,, 75.47 MHz): 6 =125.97 (quint, Ru-CsC, ,J(P, C)=15.2 Hz), 93.48 (s, Ru-C-C), 80.24, 76.51, 63.79 (s, Ru-CrC-C=C-CPh,j; IR (KBr): ;[cm-'] = 2024 (m, C=Cj, 2176 (s, C e C j . Correct elemental analysis (C, H, CIY 4 : 31P(iH) NMR (CD,CI,, 121.50 M H ~) : 6 = -11.72 (s, pph,); 13C{1H} NMR (CD,Cl,, 75.47 MHz): 6 = 252.76 (quint, Ru=C, ,J(P,C) =13.5 Hz), 155.71 (s, =CPh,), 154,15 (s, Ru=C=C=C), 150.18 (quint, Ru=C=C, tal analysis (C, H). 6 : A solution of 5 (0.62 g, 2 mmol) and N H ; ~~, (3 mmolj in 60 m~ of dichloromethane was added to 1 (0.47g. 0.5mmol) and NaPF, (0.34g, new oxide has been confirmed beyond doubt by X-ray analysisr'l and energy-dispersive electron beam microanalysis.[21
We have previously indicated that the characteristic separation of the silver partial structure (by the formation of short silver-silver contacts) and the anionic parts in silverrich oxides can only be understood if attractive interactions are assumed between the Aa+ ions despite the closed dtO 3J(P.C) = 2.2 Hzj; I3C NMR (CD,CI,, 75.47 MHz): 6 =124.43 (d, CH=, 'J(C,H) =163.8 Hzj; IR (KBr): v[cm-'] =1955(s, C=C=Cj. Correctelemen-2 mmol). The solution was stirred at room temperature for 4 h, and its color changed from orange to brown. The crude product was filtered through 30 g of alumina with ether. Recrystallization from THF/pentane (1 :3) gave 0.18 g (24%) of 6 as yellow crystals. 31P{1H) NMR (CD,CI,, 121.50MHz): 6 = -4.21 (s, PPh,); 13C{'H} NMR (CD,C1,,75.47 MHzj: 6 =131.18 (quint, C=C-C=C-CPh,). Correct elemental analysis (C, H, P). 7: To a solution of 6 (90 mg, 0.06 mmol) in 20 mL of methanol was added HBF, . Et,O (0.6 mmol). The yellow solution immediately turned blue and then violet. The reaction mixture was stirred for 2 h, the solvent was removed, and the product was washed with ether. Recrystallization from dichloromethane hexane ( I :2) afforded 70 mg (76%) of violet crystals of 7. 3'P{'H) 75.47 MHz): d = 233.68 (quint, Ru=C, 'J(P,C) = 14.3 Hz), 165.58 (s, = O h , ) , 164.96 (s, Ru=C=C=O, 138.93 (quint. Ru=C=C, 'J(P,C) =1.6 Hzj; I3C (KBr): ^v [cm-l] =1958 (s, C=C=Cj. Correct elemental analysis (C, H, P).