Linking of Cu^I Units by Tetrahedral Mo₂E₂ Complexes (E=P, As)

Abstract

The reaction of [Cp 2 Mo 2 (CO) 4 (m,h 2:2-E 2)] (A:E= P, B:E = As, Cp = C 5 H 5)w ith the WCA-containing Cu I salts ([Cu(CH 3 CN) 4 ][Al{OC(CF 3) 3 } 4 ](CuTEF, C), [Cu(CH 3 CN) 4 ][BF 4 ] (D)a nd [Cu(CH 3 CN) 3.5 ][FAl{OC 6 F 10 (C 6 F 5)} 3 ](CuFAl, E)) affords seven unprecedented coordination compounds. Depending on the E 2 ligand complex, the counter anion of the coppers alt and the stoichiometry,f our dinuclear copper dimers and three trinuclearc opper compounds are accessible. The latter complexes reveal first linearC u 3 arrays linked by E 2 units (E = P, As) coordinated in an h 2:1:1 coordination mode. All compounds were characterizedb yX-ray crystallography, NMR and IR spectroscopy, mass spectrometry and elemental analysis. To definet he nature of the Cu•••Cu•••Cu interactions, DFT calculations were performed.

Cu(I) Complexes Comprising tetrahedral Mo2E2 or Mo2PE units (E=P, As, Sb) as Chelating Ligands

“…According to the CSD database, [16] η 2 ‐coordination mode of E was also observed in four compounds, namely [( E )(μ‐CuX)] 2 (X=Cl, Br), [( E )(μ‐CuI 2 )] ∞ and [Cu 2 (η 2 ‐ E )(η 2 : 1 ‐ E ) 3 ][GaCl 4 ] 2 . 12a] Note that the only example of η 2 ‐side‐on coordinated D was observed in [(MeCN) 2 Cu 2 {(μ,η 2 : 2 ‐( D )} 2 )(Cu){μ,η 2 : η 2 : η 1 : η 1 ‐( D ) 2 }][BF 4 ] 3, [12d] which is why 4 represents only the second example to date. Both the E−E bond distances found in 4 (As1‐As1’ 2.3808(2) Å) and 5 (Sb1–Sb2: 2.75039(13) Å) are longer than that of free D and E , but comparable to the related compounds shown in Chart 1.…”

Potential of Mixed Dipnictogen Molybdenum Complexes in the Self-Assembly of Thallium Coordination Compounds

“…Current approaches in supramolecular chemistry focus on the use of nitrogen-, oxygen-, and/or sulfur-containing organic linkers to connect different metal centers. − During the last decades, our group has demonstrated that organometallic E n (E = heavier group 15 element) ligand complexes are excellent building blocks for supramolecular assemblies as well . Indeed, many examples of the coordination chemistry of E n ( n = 1–6) ligand complexes toward coinage metal salts, also in combination with organic linkers, were reported during the past two decades. , This novel approach allowed the synthesis of a large library of aggregates including polymeric (1D, − 2D , and 3D coordination polymers) and discrete (monomeric, dimeric or spherical aggregates − as well as nanobowls) supramolecular assemblies. While the coinage metal salts of Cu I /Ag I /Au I have already been extensively utilized in these studies, the monovalent ions of the heavier group 13 elements, namely In I and Tl I , have only recently attracted general interest within the field of supramolecular chemistry.…”

“… 5 Indeed, many examples of the coordination chemistry of E n ( n = 1–6) ligand complexes toward coinage metal salts, also in combination with organic linkers, were reported during the past two decades. 6 , 7 This novel approach allowed the synthesis of a large library of aggregates including polymeric (1D, 8 − 10 2D 11 , 12 and 3D 13 coordination polymers) and discrete (monomeric, 14 dimeric 15 or spherical aggregates 16 − 18 as well as nanobowls 19 ) supramolecular assemblies. While the coinage metal salts of Cu I /Ag I /Au I have already been extensively utilized in these studies, the monovalent ions of the heavier group 13 elements, namely In I and Tl I , have only recently attracted general interest within the field of supramolecular chemistry.…”