Facile entrapment of a hydride inside the tetracapped tetrahedral Cu(I)8 cage inscribed in a S12 icosahedral framework.

Reaction of [Cu(CH(3)CN)(4)](PF(6)) and NH(4)[S(2)P(OR)(2)] in a 4:3 ratio in acetone at room temperature produces octanuclear dicationic copper complexes [Cu(8){S(2)P(OR)(2)}(6)](PF(6))(2) (R = (i)Pr, 1; Et, 3) in 81 and 83% yields, respectively. On the other hand, reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[S(2)P(OR)(2)], and NaBH(4) in an 8:6:1 molar ratio in THF for 1 h yields [Cu(4)(H)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2a; Et, 4a) in 87 and 82% yields, respectively. In a similar reaction when NaBD(4) is used instead of NaBH(4), [Cu(4)(D)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2b; Et, 4b) are obtained in 83 and 78% yields, respectively. Structural elucidations of 2a and 4a reveal the tetracapped tetrahedral Cu(8) cage with an interstitial hydride. Each of the Cu(I) centers is trigonally coordinated by three S atoms, and each of the six dithiophosphate ligands is connected to a Cu(4) butterfly, where the hinge positions are occupied by two copper atoms situated at the vertex of the central tetrahedron and the wingtips are two capping Cu atoms. The 12 S atoms out of the six ligands constitute an icosahedron around the hydride-centered tetracapped tetrahedral Cu(8) framework. Surprisingly, empty Cu(8) clusters 1 and 3 can abstract hydride (or deuteride) from NaBH(4) (or NaBD(4)) in THF to form 2a and 4a (or 2b and 4b), respectively. Apparently the cubic Cu(8) core, which is known to be formed in the reaction of Cu(I) salt and dichalcogenophosph(in)ate ligands, undergoes a tetrahedral contraction due to the strong Cu...H interactions. Interestingly, the chloride can also be replaced from the chloride-centered Cu(8) complex of [Cu(8)(Cl){S(2)P(OEt)(2)}(6)](PF(6)) by hydride (or deuteride) to form 2a and 4a (or 2b and 4b). However, the hydride- and deuteride-centered compounds 2a,b and 4a,b do not allow the guest exchange.