Supporting Information

© Wiley-VCH 2007

69451 Weinheim, Germany

Unexpected reactions of Ag(NCCH3)3 [(V2O3)2(RPO3)4⊂F] with H2 and NO

Jabor K. Jabor, Reinhard Stößer, Nguyen Huu Thong, Burkhard Ziemer and Manfred Meisel* Experimental Section: 1H, 13C, 19F, 31P NMR spectra were measured on DPX 300 and 51V spectra on Bruker AV 400. ESR spectra were measured on ERS 300 (ZWG/ Magnettech GmbH, Berlin-Adlershof, Germany) KF and PhPO3H2 (Aldrich) AgNO3 (Merck) were used as supplied, HVO3 was prepared from heating NH4VO3 at 200 0C for two h. Ag(NCCH3)3 [(V2O3)2(PhPO3)4⊂F] was prepared from solvothermal reaction of HVO3, PhPO3H2, AgNO3 in CH3CN. The yield was low due to the low solubility of HVO3 in CH3CN and due to the formation of Ag(Ag-NCCH3)[PhP(O)2OP(O)2Ph]. The utility of this method has been proved by the preparation of new complexes such as [Ag(1-methyl-imidazole)2]2 [(V2O3)2(PhPO3)4⊂F], [NiCl(2,2'-bipyridyl)2]2

[(V2O3)2(PhPO3)4⊂F], [Ni(2,2'-bipyridyl))3] [(V2O3)3(PhPO3)4⊂F], and [Ni(2,2’-bipyridyl))3][(V2O3)3(tBuPO3)4⊂F] which were characterized by single crystal X-ray analysis. Concerning the solid state, compound 1 was characterized by C.H.N analysis, TGA and X-ray diffraction while further physical and chemical properties were studied by EPR using VIV as monitors. Elemental analysis (%) calc. for C30H29AgFN3O18P4V4 (1174.09 g/mol): C 30.69, H 2.49, N 3.58; found: C 30.67, H 2.55, N 3.58. Thermal analysis: Thermal analysis of compound 1 shows six steps of weight loss. The first three weight losses, which were attributed to the removal of Ag coordinated CH3CN molecules associated with endothermic processes (DTA at 120 0C 222 0C and 278 0C respectively) (observed 2.97 %, 3.97 % and 3.73 %; calculated 3.50 % for each CH3CN). The total weight loss of CH3CN is 10.67 %, which is in good agreement with the calculated value (10.49 %). The other weight losses, which may be attributed to releasing of F- and pyrolysis of organic fragment associated with exothermic processes (DTA at 319 0C, 445 0C and 579 0C respectively).

X-ray: Table 1. Crystal data and structure refinement for Ag(NCCH3)3[(V2O3)2(PhPO3)4⊂F] (1). Empirical formula C30 H29 Ag F N3 O18 P4 V4 Formula weight 1174.07 Temperature 180(2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic, C 2/c Unit cell dimensions a = 15.739(4) Å α = 90 deg. b = 14.931(3) Å β = 101.32(3) deg. c = 36.363(7) Å γ = 90 deg. Volume 8379(3) Å3 Z, Calculated density 8, 1.861 Mg/m3 Absorption coefficient 1.552 mm-1 F(000) 4656 Crystal size 0.48 x 0.40 x 0.36 mm Theta range for data collection 2.38 to 24.25 deg. Limiting indices -18<=h<=18, -17<=k<=17, -41<=l<=41 Reflections collected / unique 24056 / 6671 [R(int) = 0.0980] Completeness to theta = 24.25 98.2 % Max. and min. transmission 0.6049 and 0.5229 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 6671 / 0 / 606 Goodness-of-fit on F2 1.037 Final R indices [I>2sigma(I)] R1 = 0.0510, wR2 = 0.0951 R indices (all data) R1 = 0.0676, wR2 = 0.1039 Extinction coefficient 0.00010(4) The crystal structure has been deposited at the Cambridge Crystallographic Data Centre and allocated the deposition number CCDC 634598

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Figure 6. The effect of NO on the ESR signal intensity of [(V2O3)2(PhPO3)4⊂F]2- cage in CH3CN at 300 K.

Figure 5. ESR spectra of 1 after different thermal treatment under a) air b) H2 flow. Reference: (MgO:Cr3+g=1.9796),

Field range for all spectra: 240-400 mT

Figure 3. ESR spectra of compound 1 at room temperature, a) under air. b) under flow of H2 c) after addition of NO(g) to reaction mixture of b.