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Inorg Chem. 2002 Dec 16;41(25):6633-45.

Variable coordination modes of NO2(-) in a series of Ag(I) complexes containing triorganophosphines, -arsines, and -stibines. Syntheses, spectroscopic characterization (IR, 1H and 31P NMR, electrospray ionization mass), and structures of [AgNO2(R(3)E)(x)] adducts (E = P, As, Sb, x = 1-3).

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Dipartimento di Scienze Chimiche, Università degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy.


Adducts of triorganophosphine, triphenylarsine, and triphenylstibine with silver(I) nitrite have been synthesized and characterized both in solution ((1)H, (31)P NMR) and in the solid state (IR, single-crystal X-ray structure analysis). In addition aggregates of AgNO(2) and ER(3) (E = P, As, Sb) have been identified in solution by electrospray ionization mass spectrometry (ESI-MS). The topology of the structures in the solid state was found to depend on the nature of ER(3) and on the stoichiometric ratio AgNO(2):ER(3). The adducts AgNO(2):EPh(3) (1:1) (E = P or Sb) are one-dimensional polymers, the role of NO(2)(-) being to bridge successive metal atoms by coordination of the two oxygens to one silver atom and the nitrogen lone pair to a successive Ag. The adduct AgNO(2):P(o-tolyl)(3) (1:1) is mononuclear, due to steric hindrance of the phosphine, the nitrite being O,O'-bidentate, a rare example of a quasi-linear P-Ag-X array. AgNO(2):P(p-F-C(6)H(4))(3) (1:1) is a dimer, the nitrite being coordinated through both oxygens, the first unidentate, the second bridging bidentate. P(o-tolyl)(3) and Pcy(3) form 1:2 adducts, also mononuclear, the nitrite still an O,O'-chelate. In contrast, the adduct AgNO(2):AsPh(3) (1:2) is a centrosymmetric dimer, essentially an aggregate of a pair of [Ag(O(2)N)(AsPh(3))(2)] arrays with one nitrite oxygen being the bridging atom. The adducts AgNO(2):EPh(3) (1:3) (E = As, Sb) are mononuclear, the nitrite behaving as a consistently strong O,O'-chelate. The E = As adduct is a triclinic solvated form, whereas the unsolvated E = Sb species is monoclinic. ESI-MS spectra of acetonitrile solutions of these complexes show the existence of [Ag(ER(3))](+), [Ag(CH(3)CN)](+), [Ag(CH(3)CN)(2)](+), [AgCl(2)](-), [Ag(NO(2))(2)](-), [Ag(ER(3))(CH(3)CN)](+), and [Ag(ER(3))(2)](+) as well as higher aggregates [Ag(2)(NO(2))(ER(3))(2)](+), [Ag(2)(NO(2))(3)](-) and [Ag(2)Cl(2)(NO(2))](-), which are less prevalent.

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