The cyclic "silver-diphos" motif [Ag2(mu-diphosphine)2]2+ as a synthon for building up larger structures

The dinuclear, cyclic structural motif Ag2(diphosphine)2](2+), here termed the "silver-diphos" motif, previously observed in many diphosphine-silver complexes, has been investigated as a synthon for building up larger structures such as coordination cages and polymers. A series of ligands containing one to four meta-substituted diphosphine groups, attached via a central core, has been synthesized from the corresponding fluoroarenes by reaction with KPPh2. Upon reaction with silver salts, the target synthon is adopted by meta-substituted diphosphines 1,3-bis(diphenylphosphino)benzene (L1), 2,6-bis(diphenylphosphino)benzonitrile (L2), and 3,5-bis(diphenylphosphino)benzamide (L3), each of which gives a single species in solution consistent with the expected dimeric complexes Ag2L2(anion)2]. X-ray crystal structures of Ag2(L1)2(OTf)2] and Ag2(L2)2(SbF6)2] confirm the adoption of the silver-diphos motif in the solid state. Amide-functionalized diphosphine L3 forms a hydrogen-bonded chain structure in the solid state via the amide group. A discrete boxlike cage Ag4(L4)2]SbF6]4 based on two silver-diphos synthons is formed when the tetraphosphine Ph2Sn{3,5-bis(diphenylphosphino)benzene}2 (L4) reacts with silver(I). Its single-crystal X-ray structure reveals a central cavity of minimum diameter, ca. 5.0 A, which contains a single SbF6(-) counterion disordered over two sites. In contrast to the highly selective behavior of the di- and tetra-phosphines L1-L4, the heptaphosphine P{3,5-bis(diphenylphosphino)benzene}3 L5 and the hexaphosphine PhSn{3,5-bis(diphenylphosphino)benzene}3 L6 give dynamic mixtures upon reaction with silver salts in solution. This nonspecific behavior is rationalized by the fact that their diphosphine groups are not appropriately disposed to form stable discrete structures based on the silver-diphos synthon. By contrast, the octaphosphine Sn{3,5-bis(diphenylphosphino)benzene}4 L7 does selectively form a single, discrete, highly symmetrical product in solution, Ag4(L7)(OTf)4]. In this case, the ligand unexpectedly adopts an interarm tetra-chelating coordination mode, resulting in a continuous 24-membered ring around the periphery of the molecule. To understand the adoption of this unusual coordination mode, the alternative diphosphine Ph2Sn(3-diphenylphosphinobenzene)2 L8, which models a single interarm chelating site of L7, was also investigated. By contrast to L7, its coordination was nonspecific, giving mixtures of silver complexes upon reaction with AgOTf. The selective interarm chelation by L7 may therefore be stabilized by the continuous coordination ring in Ag4(L7)(OTf)4]; that is, the four chelating sites can be thought of as acting in a cooperative manner. Alternatively, interarm steric repulsions between phenyl groups may favor interarm chelation. Overall, we conclude that, if the diphosphine groups are appropriately articulated to act independently (i. e., they are adequately separated and oriented), the silver-diphos synthon can be a useful tool for the coordination-based self-assembly of larger structures.