Structure, photophysical properties, and DFT calculations of selenide-centered pentacapped trigonal prismatic silver(I) clusters.

Undecanuclear silver clusters [Ag(11)(mu(9)-Se)(mu(3)-Br)(3){Se(2)P(OR)(2)}(6)] (R = Et, (i)Pr, (2)Bu) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 4:3:1 in CH(2)Cl(2) at -20 degrees C. Clusters were characterized by elemental analysis, NMR spectroscopy ((1)H, (31)P, and (77)Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative. Structural elucidations revealed that the Ag(11)Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (mu(2), mu(2)) coordination mode, and three mu(3)-bromide anions.

Selenium-centered, undecanuclear silver cages surrounded by iodo and dialkyldiselenophosphato ligands. Syntheses, structures, and photophysical properties.

Three clusters [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}6] (R = Et, 1; iPr, 2; 2Bu, 3) were isolated from the reaction of [Ag(CH3CN)4](PF6), NH4[Se2P(OR)2], and Bu4NI in a molar ratio of 4:3:1 in CH2Cl2 in 47-55% yield. Compounds 1 and 2 can also be synthesized with high yield from the reaction of Ag10(Se)[Se2P(OR)2]8 with 8 equiv of Bu4NI. In the positive fast atom bombardment mass spectra of 1-3, two major peaks that correspond to the intact molecule with the loss of an iodide ion, [Ag11(mu9-Se)(mu3-I)(2){Se2P(OR)2}6]+, and a diselenophosphate ligand, [Ag11(mu9-Se)(mu3-I)3{Se2P(OR)2}5]+, were identified.