Solvent effects on the reactions of copper chlorides with OP(NH-t-Bu)₃ — Formation of the novel [Cu₅Cl₁₀]^5– anion via in situ templation

Abstract

X-ray structural investigations have shown that the products of the reaction of CuCl 2 ·2H 2 O and OP [NH-t-Bu] 3 are markedly dependent on solvent and temperature. The polymeric ionic complex [(t-BuNH 3 ) 2 (Cu 3 (OH)(H 2 O)Cl 7 )] ∞ (1), containing a trinuclear anionic repeating unit, is obtained from toluene at 80°C, whereas the 2:1 adduct Cu(t-BuNH 2 ) 2 Cl 2 (4) is formed at 150°C. By contrast, a neutral tetranuclear cluster Cu 4 [PO(NH-t-Bu) 3 ] 4 (µ 4 -O)Cl 6 (2) or the one-dimensional chain [Cu(Py) 2 Cl 2 ] ∞ (3) is produced when the reaction is carried out in hexane or pyridine, respectively, at 80°C. The reaction of a mixture of CuCl and CuCl 2 ·2H 2 O (2:1 molar ratio) with OP[NH-t-Bu] 3 at 80°C in toluene produces [t-BuNH 3 ] 5 [Cu 5 Cl 10 ] (5), in which the anion is a pentanuclear cluster with both terminal and bridging chloride ions. The removal of the chloride ions from the reaction mixture by the addition of AgNO 3 yields the 2:1 adduct Cu[OP(NH-t-Bu) 3 ] 2 (NO 3 ) 2 (6). Résumé :Des études par diffraction des rayons X ont montré que les produits obtenus par réaction du CuCl 2 ·2H 2 O et le OP[NH-t-Bu] 3 dépendent fortement du solvant et de la température. Le complexe ionique polymère [(t-BuNH 3 ) 2 (Cu 3 (OH)(H 2 O)Cl 7 ] 4 (1) contenant une maille élémentaire anionique trinucléaire est obtenu à partir du toluène à 80°C alors que l'adduit 2:1 Cu(t-BuNH 2 ) 2 Cl 2 (4) est le produit qui se forme à 150°C. Par opposition à ces résultats, lorsqu'on effectue les réactions dans l'hexane ou la pyridine à 80°C, ce sont respectivement un agrégat tétra-nucléaire neutre de formule Cu 4 [PO(NH-t-Bu) 3 ] 4 (µ 4 -O)Cl 6 (2) et la chaîne unidimensionnelle [Cu(Py) 2 Cl 2 ] 4 (3) qui se forment. La réaction d'un mélange de CuCl et de CuCl 2 ·2H 2 O (rapport molaire de 2:1) avec le OP[NH-t-Bu] 3 , à 80°C dans le toluène, conduit à la formation de [t-BuNH 3 ] 5 [Cu 5 Cl 10 ] (5) dans lequel l'anion est un agrégat pentanucléaire dans lequel les anions terminaux et formant le pont sont des chlorures. L'élimination des ions chlorures du mé-lange réactionnel par addition de AgNO 3 conduit à la formation de l'adduit 2:1 Cu[OP(NH-t-Bu) 3 ] 2 (NO 3 ) 2 (6).

The hydrogen-bonded dimers ofN,N′,N′′-tricyclohexylphosphoric triamide in new tin(IV) and copper(II) complexes

“…The P atoms in the PTA ligands adopt a slightly distorted tetrahedral environment and the Cu-O-P angle is a little under 140 . These geometric parameters are consistent with those in related structures: Fu & Chivers, 2007) and [CuCl 2 (NHC 4 H 8 O){(O)P(NMe 2 ) 3 } (YIBZEP; Xie et al, 2007).…”

The neutral cluster amminehexa-μ2-chlorido-μ4-oxido-tris(1,4,6-triazabicyclo[3.3.0]oct-4-ene)tetracopper(II)

“…Other nonbridging ligands may be attached to copper(II), such as halides (Jackson et al, 1996;Belford et al, 1972;Fu & Chivers, 2007;Harlow Simonsen, 1977), oxygen-bonded ligands (Churchill & Rotella, 1979;Bertrand & Kelley, 1966), nicotine (Haendler, 1990), oxoamines (Weinberger et al, 1998), pyridine (Nä ther & Jess, 2002;Gill & Sterns, 1970;Duncan et al, 1996;Kilbourn & Dunitz, 1967), imidazole (Zhang et al, 2003;Norman et al, 1989;Erdonmez et al, 1990;Clegg et al, 1988;Corté s et al, 2006), pyrazole (Keij et al, 1991;Liu et al, 2003), triazole (Skorda et al, 2005), tetrazole (Lyakhov et al, 2004), azaindole (Poitras & Beauchamp, 1992), phosphine (Bertrand, 1967), thiazole (Bolos & Christidis, 2002), sulfimide (Kelly et al, 1999), phosphite (Churchill et al, 1975) or sulfoxide (Brownstein et al, 1989;Guy et al, 1988).…”

Solvothermal Synthesis and Crystal Structure of A Supramolecular Compound Tris(tert-butylamino)chlorophosphonium Chloride

“…The preparation and structural characterization of imido analogues of common phosphorus oxoanions is an active area of main group chemistry [1][2][3][4] . Chivers et al 5 found that OP(NHt-Bu) 3 could be protonated and converted to a cation under hydrothermal condition with CuCl 2…”

“…Armstrong et al 6 had also investigated the reaction of OP(NHt-Bu) 3 and ZnMe 2 and successfully synthesized some novel zinc cluster compounds exhibited interesting molecular structure. Being motivated these researches, we employed OP(NHt-Bu) 3 , ZnCl 2 and hydrochloric acid as reactor to synthesize novel zinc coordinated compound, but a new organic phosphorous cation compound featured as a supramolecular structure was obtained (Scheme-I). During the past decades, a large number of supramolecular structures have been assembled and characterized due to their interesting structure and many respected applications in sensors, catalysis, optical/optoelectronic and magnetic materials etc.…”