Metallorganische Verbindungen des Kupfers. Synthese und Struktur von Komplexen des 3,3,6,6-Tetramethyl-1-thia-4-cycloheptins mit Kupfer(I)-Alkoxiden und -Carboxylaten

Olbrich, Falk; Behrens, Ulrich; Gröger, Gunther; Weiß, Erwin

doi:10.1016/0022-328x(93)80096-t

Cited by 26 publications

(8 citation statements)

References 11 publications

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“…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].…”

Section: Exhibits Such An Example ([Cu 4 I 4 ]L1supporting

confidence: 87%

“…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].…”

Section: Introductionmentioning

confidence: 99%

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Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

et al. 2018

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The reactivity of the tetradentate ligand bis(p-thiomethylphenylacetylene) (MeSC 6 H 4 C≡C-C≡CC 6 H 4 SMe; L2) towards the CuI salt is compared to that for the known organometallic analogue trans-bis(p-thiomethylethynylbenzene)bis(trimethylphosphine)platinum(II) (trans-Pt(PMe 3) 2 (C≡CC 6 H 4 SMe) 2 ; L1). While L1 with CuI form a highly luminescent porous 2D coordination polymer (CP) of general formula ([Cu 4 I 4 ]L1 • EtCN) n (CP1; Juvenal et al. in Inorg Chem 55:11096-11109, 2016) exhibiting both Cu(η 2-C≡C) and Cu-S bonds, L2 reacts with CuI to produce a luminescent non-porous 2D CP exhibiting the general formula ([Cu 4 I 4 ]{L2} 3) n , CP2, which does not use the highly expected Cu(η 2-C≡C) linkage, relying strictly upon Cu-S coordination. An examination of the X-ray structures for both L2 and CP2 indicates that CP2 network is built upon an expansion of the L2 lattice (plane sliding and slight L2-L2 distance separation) resembling to a sort of template effect. CP2 has been characterized by TGA, UV-Vis, emission spectroscopy, and photophysics, which are accompanied by DFT and TDDFT computations.

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Section: Exhibits Such An Example ([Cu 4 I 4 ]L1supporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

et al. 2018

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“…The C−C distances of the bridging acetylenes (1.29(1) and 1.31(1) Å) and the Cu−C distances (1.95(1)−1.99(1) Å) are comparable to those in other μ-acetylene copper complexes, while Cu−Cu distances (2.621(2) and 2.635(2) Å) are slightly shorter (cf. C−C, 1.29 ± 0.03 Å; Cu−C, 1.96 ± 0.04 Å; Cu−Cu, 2.8 ± 0.1 Å) . However, 6 is the only complex in this group that does not contain additional ligands bridging the copper centers, and the Cu−Cu distances in 6 are still well in the usual range observed for dicopper complexes in general.…”

Section: Resultsmentioning

confidence: 75%

π Back-Bonding in Dibenzyl-β-diketiminato Copper Olefin Complexes

Oguadinma

Schaper

2009

Organometallics

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N,N'-Dibenzyl-4-amino-2-iminopent-3-ene, nacnac Bn H, was obtained in a one-step synthesis starting from benzylamine and acetylacetone. Reaction of nacnac Bn H with CuOtBu in the presence of various Lewis bases gave the corresponding copper complexes (nacnac Bn )CuL (L: 2, styrene; 3, η 2acrylonitrile; 4, allyl phenyl ether; 5, stilbene; 7, xylylisonitrile; 8, triphenylphosphine). With diphenylacetylene (DPA) the dimeric complex {(nacnac Bn )Cu} 2 (μ-DPA), 6, was obtained. In the presence of excess DPA, 6 coordinates additional acetylene to form the monomeric complex (nacnac Bn )Cu(DPA), 6b. All complexes, with the exception of 4 and 6b, were characterized by X-ray diffraction studies. Structural and spectroscopic data indicate that π back-bonding in 2-8 is still weak when compared to other transition metals, but stronger than in most Cu(I) complexes. Olefin exchange experiments indicate preferred binding of electron-deficient olefins. Reaction of 3 with morpholine did not yield any hydroamination products, in agreement with significant π backbonding toward the olefin.

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“…In the case of complexes 4a , b , the connectivity of the complex is dictated by the familiar coordinative tetra- – O 2 CCF 3 motif. Although literature concerning the interactions between Ag + and alkynes in the presence of bidentate anions such as – O 2 CCF 3 is quite sparse, , far more work exists for Cu + complexes. − This work demonstrates that internal alkynes are able to compete to some degree with the bidentate anions – O 2 CR (R = Me, Ph, CF 3 ) for coordination to Cu + , resulting in complexes of type F or closely related derivatives.…”

Section: Resultsmentioning

confidence: 93%

Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

et al. 2015

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A number of group 11 salts, [MX] (M = Ag, X– = –O3SCF3, –O2CCF3, BF4 –; M = Cu; X = Cl, Br) and [Cu(MeCN)4][PF6], were found to react in varying stoichiometries with ethyne-1,2-diyl compounds, [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] (R = H, Me), to give a number of complex cations. The trication salts [Ag3({Ru(CO)2(η-C5H4Me)}2(μ2-η1:η1-CC))3](O3SCF3)3, [Ag3({Ru(CO)2(η-C5H4R)}2(μ2-η1:η1-CC))({Ru(CO)2(η-C5H4R)}2(μ2-η1:η2-CC))2](BF4)3, and [Cu3({Ru(CO)2(η-C5H4R)}2(μ2-η1:η2-CC))({Ru(CO)2(η-C5H4R)}2(μ2-η2-CC))](PF6)3 result from the use of the respective anion salts in their syntheses. Coordination of Ag+ by the ethyne-1,2-diyl complexes in the presence of F3CCO2 – yields the tetranuclear complexes [Ag4({Ru(CO)2(η-C5H4R)}2(μ2-η2-CC))2](μ2-O2CCF3)4 (R = H, Me). The reaction of CuCl does not afford the discrete dimeric complexes normally observed for internal alkynes and metal alkynyl complexes but, rather, the 1-D polymer [Cu2(μ-Cl)2({Ru(CO)2(η-C5H4R)}2(η2-CC))](∞|∞), while CuBr gives the discrete dimer motif known in the literature. The solution structures at 1/2, 1/1, and 2/1 stoichiometries of Ag+/[{Ru(CO)2(η-C5H5)}2(μ2-CC)] have been probed spectroscopically, and the {Ru(CO)2(η-C5H4R)} environments appear to be equivalent and, likewise, the resonances attributable to their CC units. In a subsequent reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] and AgBF4 use of a strict Ag+/ethyne-1,2-diyl ratio gave [Ag({Ru(CO)2(η-C5H5)}2(η2-CC))2](BF4). The analogous Cu+ adduct [Cu({Ru(CO)2(η-C5H5)}2(η2-CC))2](PF6) is observed, along with the tricopper(I) adduct from the reaction of [{Ru(CO)2(η-C5H4R)}2(μ2-CC)] and [Cu(NCMe)4](PF6). A combination of factors appears to control the solid-state structures of these coinage metal adducts, with the anion found to be that which influences the packing to the greatest extent.

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Metallorganische Verbindungen des Kupfers. Synthese und Struktur von Komplexen des 3,3,6,6-Tetramethyl-1-thia-4-cycloheptins mit Kupfer(I)-Alkoxiden und -Carboxylaten

Cited by 26 publications

References 11 publications

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

π Back-Bonding in Dibenzyl-β-diketiminato Copper Olefin Complexes

Anion-Directed Solid-State Structures of Copper(I) and Silver(I) Adducts of Ruthenium Ethyne-1,2-diyl Compounds

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