Three clusters 1-3, Cu(8)(mu8-Cl)[Se(2)P(OR)(2)](6)(PF(6)) (R= Et, Pr, (i)Pr), were synthesized in high yield from the reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NCl in a molar ratio of 4:3:1 in diethyl ether. FAB mass spectra show m/z peaks at 2218.10 for 1, 2386.10 for 2, and 2387.34 for 3 which are due to molecular cations, [1-PF(6)]+, [2-PF(6)]+, and [3-PF(6)]+, respectively. (31)P NMR spectra of 1-3 display a singlet at delta 76.48, 76.73, and 69.32 ppm with satellites (J(PSe) = 652, 653, and 648 Hz), respectively. The (77)Se NMR spectra of 1-3 exhibit a doublet peak at -21.7, -16.42, and 2.3 ppm, respectively (J(SeP) = 652 Hz for 1, 653 Hz for 2, and 648 Hz for 3). The X-ray structure (1-3) consists of a discrete cationic cluster in which eight copper ions are linked by six diselenophosphate ligands and a central mu8-Cl ion with a noncoordinating PF(6)(-) anion. The shape of the molecule is a chloride-centered distorted Cu(8) cube in clusters 1 and 2 and a near perfect Cu(8) cube for cluster 3. The dsep ligand exhibits a tetrametallic tetraconnective (mu2, mu2)) coordination pattern, and each occupies a square face of the cube. Each copper atom of the cube is coordinated by three selenium atoms with a strong interaction with the central chloride ion. The observed Cu-Cl distances lie in the range 2.649-2.878 A.

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Most of the structures containing hexaselenodiphosphate(iv), P 2 Se 6 4À , are ternary and quaternary solid-state materials. In addition to the high-temperature reactions of the metals with P and Se, these compounds are usually synthesized by the application of the polychalcophosphate flux method. Notable examples of ternary phases are M 2 P 2 Se 6 (M Pb, [1a] Hg [1b] ) and Tl 4 P 2 Se 6[1c] from Brockner et al., M 4 (P 2 Se 6 ) 3 (M Sb, Bi) [2] , and Ag 4 P 2 Se 6 . [3] The quaternary phases are a,b-KMP 2 Se 6 (M Sb, Bi),

A Novel Nonacoordinate Bridging Selenido Ligand in a Tricapped Trigonal-Prismatic Geometry. X-Ray Structure of Cu 11 (µ 9 -Se)(µ 3 -Br) 3 [Se 2 P(OiPr) 2 ] 6 .-The title compound (III) is characterized by FAB mass spectroscopy, 1 H, and 31 P NMR spectroscopy. As revealed by XRD, the yellow compound (III) crystallizes in the triclinic space group P1 with Z = 2. It contains a nonacoordinate bridging selenido ligand in a tricapped trigonal prismatic copper environment. The Cu 11 Se core is stabilized by three bromide and six dsep ligands. The colorless compound (V) crystallizes in the monoclinic space group C2/c with Z = 4. It consists of a bromide-centered Cu I 8 cube of which each edge is bridged by a Se atom of the dsep ligands. -

The coexistence of P4+ and P5+ in one complex and the presence of an ethane‐like hexaselenodiphosphato ligand, P2Se64−, are the novel features of the title compounds (see structure, in which R=Et or iPr; OR groups omitted for clarity). The coordination mode of P2Se64− in these dodecanuclear copper species is unprecedented and has not even been identified in any mixed ligands containing Group 15/16 elements.