Bi-, tetra-, and hexanuclear AuI and binuclear AgI complexes and AgI coordination polymers containing phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2, and pyridyl ligands

The reactions of phenylaminobis(phosphonite), PhN{P(OC6H4OMe-o)2}2 (1) (PNP), with AuCl(SMe2)] in appropriate ratios, afford the bi- and mononuclear complexes, (AuCl)2(micro-PNP)] (2) and (AuCl)(PNP)]2 (3) in good yield. Treatment of 2 with 2 equiv of AgX (X = OTf or ClO4) followed by the addition of 1 or 2,2'-bipyridine affords Au2(micro-PNP)2](OTf)2 (4) and Au2(C10H8N2)2(micro-PNP)](ClO4)2 (5), respectively. Similarly, the macrocycles Au4(C4H4N2)2(micro-PNP)2](ClO4)4 (6), Au4(C10H8N2)2(micro-PNP)2](ClO4)4 (7), and Au6(C3H3N3)2(micro-PNP)3](ClO4)6 (8) are obtained by treating 2 with pyrazine, 4,4'-bipyridine, or 1,3,5-triazine in the presence of AgClO 4. The reaction of 1 with AgOTf in a 1:2 molar ratio produces Ag2(micro-OTf)2(micro-PNP)] (9). The displacement of triflate ions in 9 by 1 leads to a disubstituted derivative, Ag2(micro-PNP)3](OTf)2 (10). The equimolar reaction of 1 with AgClO4 in THF affords Ag2(C4H8O)2(micro-PNP)2](ClO4)2 (11). Treatment of 1 with AgClO4 followed by the addition of 2,2'-bipyridine affords a discrete binuclear complex, Ag2(C10H8N2)2(micro-PNP)](ClO4)2 (12), whereas similar reactions with 4,4'-bipyridine or pyrazine produce one-dimensional zigzag Ag (I) coordination polymers, Ag2(C10H8N2)(micro-ClO4)(ClO4)(micro-PNP)]n (13) and Ag2(C4H4N2)(micro-ClO4)(ClO4)(micro-PNP)]n (14) in good yield. The nature of metal-metal interactions in compounds 2, 4, 5, and 12 was analyzed theoretically by performing HF and CC calculations. The structures of the complexes 2, 4, 5, 7, 9, 12, and 14 are confirmed by single crystal X-ray diffraction studies.