The title compound, [Cu4I4(C12H27P)4], recovered from an attempt to prepare triisopropyl­silylthiol­ato(tri‐tert‐butyl­phosphine)copper(I), is found to be tetra­meric with a distorted heterocubane structure, one of the body diagonals of the cube being a crystallographic threefold rotation axis.

The copper silanechalcogenolates tBu3PCuESiPh3 (1, E = O; 2, E = S; 3, E = Se) were prepared from the reaction of [tBu3PCu(CH3CN)3]BF4 with [Ph3SiELi(THF)2]2 in acetonitrile. The compounds were obtained as colorless, crystalline, but thermally labile solids. X-ray crystallography shows that complexes 1-3 are monomeric in the solid state with no Cu...Cu interactions. The Cu atoms have either a linear or a near-linear coordination geometry in all three complexes. Interestingly, the O atom in complex 1 is also linear, which is in contrast to the highly bent S (2) and Se analogues (3). Density functional theory calculations suggest that both the linear geometry of 1 and an associated extremely short Cu-O distance [1.769(4) A] are not the result of pi delocalization but are the result of a fine balance of electrostatic interaction and Pauli repulsion.

The mol­ecule of the title compound, C30H46, has a crystallographically imposed inversion center and the cyclo­hexyl groups are oriented with their methine H atoms pointing towards one another (H⋯H = 2.04 Å).

The mol­ecule of the title compound, C30H46, has a crystallographically imposed inversion center and the cyclo­hexyl groups are oriented with their methine H atoms pointing towards one another (H⋯H = 1.99 Å). The cyclohexyl groups adopt chair conformations. A significant C—H⋯π inter­action assembles mol­ecules into layers parallel to (100).

Bis(triphenyl­silyl)selenide, [(C6H5)3Si]2Se or C36H30SeSi2, exists in the solid state as monomeric angular mol­ecules. Si—Se—Si angles of 111.56 (3) and 109.45 (3)° are found in the two independent mol­ecules.