Metallorganische Verbindungen des Kupfers XI. Synthese und Struktur von zwei vierkernigen Alkin-μ2-Halogeno-μ4-Oxo-Kupfer(I)-Komplexen; Alkin = 3,3,6,6-tetramethyl-1-thia-4-cycloheptin

From Pyrazolate-Based Binuclear Copper(I) Complexes to Octanuclear σ-Mesityl-Bridged μ4-Oxo-Cuprocuprates: Controlled Dioxygen Splitting by Organocopper Scaffolds

“…The Cu−O bond distances of 3 − 8 are not significantly different from each other and lie in a range similar to that observed for [Cu 10 O 2 Mes 6 ] . They are, however, slightly shorter than in the complexes of the type [(μ 4 -O)Cu I 4 X 2 (TMTCH) 4 ] (averaged Cu−O bonding distances 1.908(3) Å) and also in comparison with the Cu−O bonds of cupric compounds [(μ 4 -O)Cu II 4 X 6 L 4 ]. , This may be due to the higher coordination numbers at the copper centers in those latter complexes, since in the crystal structure of cuprite (Cu 2 O), which consists of linear O−Cu−O units, short (1.848 Å) Cu−O bonding distances are also observed . The linking Cu(μ-Mes)Cu units of all these complexes 3 − 8 show typical Cu−C bond lengths and Cu−C i −Cu angles as well as Cu···Cu separations (Tables and ), which are also observed in the molecular structures of the parent [Cu 10 O 2 Mes 6 ] and [Cu 5 Mes 5 ].…”

“…A similar observation was made for the molecular structures of the complexes [(μ 4 -O)Cu I 4 X 2 (TMTCH) 4 ] (X = Cl, Br; TMTCH = 3,3,6,6-tetramethyl-1-thia-4-cycloheptyne). Herein, the two halide bridges cause the distortion by pulling two copper centers together . Although two pyrazolate capping ligands are present in 3 − 8 , they do not affect the central (μ 4 -O)Cu I 4 core in a similar way, since the mesityl bridges act as flexible “chain linkers” between the core and the peripheral binuclear pyrazolate frameworks.…”

Synthesis and Coordination Chemistry of Gold(I) Acetylides. The Solid-State Structure of {[η2-(Ph3P)AuC⋮CFc]Cu(μ-Cl)}2

“…Thus, the coordination sphere around Cu(1) is trigonal-planar and comprises the η 2 -bonded acetylide and the μ-bridging chloro ligands. A similar feature has been observed for other Cu 2 (μ-X) 2 -containing complexes (X = halide), e.g., [(η 2 -Me 3 SiC⋮CSiMe 3 ) 2 Cu 2 (μ−Br) 2 ],23a [(η 2 -PhC⋮CSiMe 3 )Cu(μ-Br)] 2 , or [(η 2 -FpC⋮CPh)Cu(μ-Cl)] 2 [Fp = (η 5 -C 5 H 5 )Fe(CO) 2 ] 18a or the copper(I) tmtch complexes prepared by Weiss and Behrens (tmtch = 3,3,6,6-tetramethyl-1-thia-4-cycloheptyne) . The C⋮C triple bond distance C(1)−C(2) amounts to 1.227(9) Å and lies in the range of bond lengths encountered in related η 2 -bonded organic or organometallic alkynes to copper(I) salts; for example, in [(η 2 -FpC⋮CPh)Cu(μ-Cl)] 2 the C⋮C bond length is 1.27(2) Å 18a.…”

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

“…When Cu-S coordinations also occur, porous or non-porous 2D frameworks are systematically generated [23,24]. This preference for Cu(η 2 -C≡C) linkage over Cu-S is again fully consistent with earlier literature observation mentioned above [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. However, very rare examples of 2D and 3D CPs produced with alkynylcontaining dithioethers (here RC 6 H 4 SCH 2 C≡CCH 2 C 6 H 4 R; R = H, CH 3 ) and CuX salts (X = I in this case) through Cu-S only, also exist (2 examples) [25,26].…”

“…There is a wealth of examples dated from the 1990's where copper halide salts selectively coordinate the alkynyl function (η 2 -C≡C) over the thioether one in bidentate (R-C ≡C•••S-R′) ligands to form organometallic species with a dandling uncoordinated thioether [1][2][3][4][5][6][7][8][9][10][11][12][13]. However, this trend does not exclude the several examples where both coordination centers are used to generate polymetallic (cyclic and acyclic) species and polymeric solids [14][15][16][17][18].…”