Reactions of 1,1′‐Diphosphaferrocene with CuCl and CuBr Resulting in Cu₄P₄X₄Fe₂ (X = Cl, Br) Complexes with Adamantane‐like Topologies 

Abstract

Cu 4 P 4 X 4 Fe 2 (X = Cl, Br) cages are formed upon reactions of octaethyl-1,1'-diphosphaferrocene (odpf) with the respective Cu I halide in CH 2 Cl 2 /CH 3 CN solvent mixtures. These cages have adamantoid Cu 4 X 4 P 2 cores with two planar anelated CuP 2 Fe rings as the flaps. Both complexes 1 and 2 feature tri-and tetracoordinate Cu I ions and an additional acetonitrile solvent molecule in the crystal. In 1, the solvent molecule is coordinated to one copper ion whereas it remains uncoor-

Synthesis and Characterization of Copper(I) Halide Complexes with N‐(2, 6‐Diisopropylphenyl)‐N′‐benzoylthiourea: Monomeric, Dimeric, and Cage Structures

“…Thus 4 exhibits Cu I ions both in tricoordinate [Cu(1) and Cu(3)] and tetracoordinate [Cu(2) and Cu(4)] mode with distorted trigonal planar and tetrahedral coordination, respectively. As expected, the Cu–S and Cu–Br bond lengths of the tricoordinate copper ions are distinctly shorter than those of the tetracoordinate ones 36. For instance in 4a , the bond lengths of Cu(1) and Cu(3) with respective bridging atoms S(1), S(3), Br(2), or Br(4) (if available) are shorter than those involving Cu(2) and Cu(4) atoms.…”

“…It has been shown that reactions between copper(I) halides and thiourea or its derivatives frequently generate a variety of complexes, which have unpredictable stoichiometry and stereochemistry 37. This structural diversity originates from the propensity of the halide to act as terminal or bridging ligand and of the thiourea ligand to coordinate in a monodentate or a bridging mode 36. In the known tetranuclear Cu I systems with sulfur donor, the adamantanoid cages often contain the Cu 4 S 6 core,38 in which simply the soft anions like halides have the chance to bind with the copper site in a terminal fashion (Cl,39 I13,37).…”

“…Also the inward bending of the copper atoms Cu(1) and Cu(3) in 4a results in a somewhat acute Cu(1)-Br(1)-Cu(3) angle of 67.60(3)°, which is very close to that in the P 4 Cu 4 Br 4 complex [66.61(5)°]. [36] The root tip bromide atom Br(1) is found to be innocent in any hydrogen bonding interaction. According to the vector moving from the top Br(3) to the Br(1), both 4a and 4b show the same direction in the cell.…”

“…As expected, the Cu-S and Cu-Br bond lengths of the tricoordinate copper ions are distinctly shorter than those of the tetracoordinate ones. [36] For instance in 4a, the bond lengths of Cu(1) and Cu(3) with respective bridging atoms S(1), S(3), Br(2), or Br(4) (if available) are shorter than those involving Cu(2) and Cu(4) atoms.…”

“…[37] This structural diversity originates from the propensity of the halide to act as terminal or bridging ligand and of the thiourea ligand to coordinate in a monodentate or a bridging mode. [36] In the known tetranuclear Cu I systems with sulfur donor, the adamantanoid cages often contain the Cu 4 S 6 core, [38] in which simply the soft anions like halides have the chance to bind with the copper site in a terminal fashion (Cl, [39] I [13,37] ). Only one comparable example involving edge-bridging bromine atoms in the P 4 Cu 4 Br 4 core with adamantane-like topology was established by treatment of 1,1Ј-diphosphaferrocene with CuBr, but with single conformation.…”