Structure of chloro[1,1,1-tris(diphenylphosphinomethyl)ethane]copper(I)

Structural and Spectroscopic Properties of New Copper(I) Complexes with 1,1,1‐Tris(diphenylphosphanylmethyl)ethane and Heterocyclic Thiolates

“…The average for Cu-P bond lengths in the two compounds [2.2934(6) Å in 1 and 2.2690(7) Å in 2] is close to the values 2.2867(17) Å and 2.2953(4) Å found in [Cu(κ 3 -triphos)Cl] [3] and in [Cu(κ 3 -triphos)Br] [4] respectively. On the other hand, each deprotonated thione ligand is bonded to the metal center in 1 and 2 with a "short" Cu-S bond length of 2.2669(6) and 2.2570(7) Å respectively, which is far from the values normally observed in other tetrahedral Cu I complexes bearing neutral pyridine-2-thione or pyrimidine-2-thione, but also from the value of 2.302(4) Å observed for [CuBr(κ 1 -py2S)(PPh 3 ) 2 ] bearing the heterocyclic thione ligand also in its deprotonated form.…”

“…The single-crystal analysis of (2) 2.2699(6) Cu(1)-P(2) 2.2816(7) Cu(1)-P (3) 2.3105 (6) Cu (1) (9) compound 1 indicates the presence of one solvent (ethanol) molecule, trapped in the crystal lattice. As shown in the ORTEP drawings the structures of compounds 1 and 2 are quite similar having in common the highly distorted tetrahedral coordination of the copper(I) centre, which is surrounded by the P atoms of the chelating [3] [Cu(κ 3 -triphos)Br] [4] and [PhCu(κ 3 -triphos)] [5] are also quite small and comparable to these observed in compound 2. Nevertheless, such distortions within all these structures could be considered as normal due to the strain imposed by the six-membered chelate rings formed.…”

“…The ability of 1,1,1-tris(diphenylphosphanylmethyl)ethane, (Ph 2 PCH 2 ) 3 CMe, (triphos) to preferably act as a tripodal ligand generating mononuclear four-coordinate copper(I) halide complexes is well known. [4] Having this in mind, we decided to approach the desired mononuclear mixed-ligand complexes starting from copper halides to ensure that coordination of triphos takes place in the established manner.…”

“…To a suspension of 0.25 mmol of copper(I) bromide (35.5 mg) in 30 cm 3 of dry acetonitrile a solution of 156 mg (0.25 mmol) of 1,1,1-tris(diphenylphosphanylmethyl)ethane in 25 cm 3 of dry acetonitrile was added and the mixture was stirred at 50°C for several hours. The resulting clear colourless solution was cooled to room temperature and then an ethanolic solution of potassium thiolate, which was prepared by treatment of 0.25 mmol of the parent thione with KOH (0.5 mL of a 0.5  ethanolic solution) was added slowly.…”

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) plexes [CuX(κ 3 -triphos)] (X = Cl, Br) [3,4] and to a few organo-copper(I) compounds, such as [CuPh(κ 3 -triphos)] [5] and [Cu(µ-CCPh)(κ 3 -triphos)] 2 . [6] In previous work we explored the molecular architectures realized by thione-ligated copper(I) halide complexes containing tertiary arylphosphanes as bulky co-ligands.…”