The AgX salts [X = Cl, Br, I, NO3] react with CP3 [MeC(CH2PPh2)3], PP3 [P(CH2CH2PPh2)3] and NP3 [N(CH2CH2PPh2)3] in 1 ∶ 1 stoichiometric ratio to afford complexes Ag(CP3)X [X = Cl (1), Br (2), I (3)], Ag(PP3)Cl (4), Ag(NP3)Cl (6) and Ag(NP3)(NO3) (7) where Ag(I) is bound to three P atoms of the ligand. The X-ray crystal structure of complex 6 consists of a mononuclear compound with absence of the N atom of NP3 in the coordination
to the metal. The 1 ∶ 1 complex obtained by reaction of AgNO3 with PP3 was shown by conductivity measurements, mass spectrometry, infrared and NMR spectroscopy to be a dinuclear ionic complex [Ag2(PP3)2](NO3)2 (5) where Ag(I) shows three- and four-coordination. The interaction of AgX halides with CP3 in 2 ∶ 1 stoichiometric ratio leads to complexes Ag2(CP3)X2 [X = Cl (8), Br (9), I (10)] which were shown by X-ray crystallography to consist of infinite zigzag (X = Cl, I) or linear (X = Br) chains containing three- and four-coordinate Ag(I) and constituting the first examples of such complexes with CP3. These polymeric chains did not give reaction
with another equivalent of AgX to form the Ag3(CP3)X3 [X = Cl, Br, I] complexes. The 2 ∶ 1 and 3 ∶ 1 nitrate derivatives Ag2(PP3)(NO3)2 (11), Ag2(NP3)(NO3)2 (12), Ag3(PP3)(NO3)3 (13) and Ag3(NP3)(NO3)3 (14) show participation of the nitrate anion as ligand finding for 13 two different geometries about Ag(I) in solution. Complexes 13 and 14 react with the corresponding phosphines PP3 and NP3 to form complexes 5
and 7, respectively involving ring-closure reactions.