Novel Chloride-Centered Discrete Cu<sup>I</sup><sub>8</sub> Cubic Clusters Containing Diselenophosphate Ligands. Syntheses and Structures of {Cu<sub>8</sub>(μ<sub>8</sub>-Cl)[Se<sub>2</sub>P(OR)<sub>2</sub>]<sub>6</sub>}(PF<sub>6</sub>) (R = Et, Pr, <sup>i</sup>Pr)<sup>1</sup>
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Three clusters 1−3, Cu8(μ8-Cl)[Se2P(OR)2]6(PF6) (R= Et, Pr, iPr), were synthesized in high yield from the reaction of [Cu(CH3CN)4](PF6), NH4[Se2P(OR)2], and Bu4NCl 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−PF6]+, [2−PF6]+, and [3−PF6]+, respectively. 31P NMR spectra of 1−3 display a singlet at δ 76.48, 76.73, and 69.32 ppm with satellites (JPSe = 652, 653, and 648 Hz), respectively. The 77Se NMR spectra of 1−3 exhibit a doublet peak at −21.7, −16.42, and 2.3 ppm, respectively (JSeP = 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 μ8-Cl ion with a noncoordinating PF6- anion. The shape of the molecule is a chloride-centered distorted Cu8 cube in clusters 1 and 2 and a near perfect Cu8 cube for cluster 3. The dsep ligand exhibits a tetrametallic tetraconnective (μ2, μ2) 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 Å.
