This article describes the structure determination of five homoleptic d(10) metal-aryl/alkylacetylides [RC triple bond CM] (M=Cu, R=tBu 1, nPr 2, Ph 3; R=Ph, M=Ag 4; Au 5) by using X-ray single-crystal and powder diffraction. Complex 1.C6H6 reveals an unusual Cu20 catenane cluster structure that has various types of tBuC triple bond C-->Cu coordination modes. By using this single-crystal structure as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data, the structure of the powder synthesized from CuI and tBuC triple bond CH was found to have the same structure as 1. Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu4 subunits connected through bridging nPrC triple bond C groups. Complex 3 forms an infinite chain structure with extended Cu-Cu ladders (Cu-Cu=2.49(4)-2.83(2) A). The silver(I) congener 4 is iso-structural to 3 (average Ag-Ag distance 3.11 A), whereas the gold(I) analogue 5 forms a Au...Au honeycomb network with PhC triple bond C pillars (Au-Au=2.98(1)-3.26(1) A). Solid-state properties including photoluminescence, nu(C triple bond C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures.

Structure Determination of Homoleptic AuI, AgI, and CuI Aryl/Alkylethynyl Coordination Polymers by X‐ray Powder Diffraction

The copper-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most broadly applicable and easy-to-handle reactions in the arsenal of organic chemistry. However, the mechanistic understanding of this reaction has lagged behind the plethora of its applications for a long time. As reagent mixtures of copper salts and additives are commonly used in CuAAC reactions, the structure of the catalytically active species itself has remained subject to speculation, which can be attributed to the multifaceted aggregation chemistry of copper(I) alkyne and acetylide complexes. Following an introductory section on common catalyst systems in CuAAC reactions, this review will highlight experimental and computational studies from early proposals to very recent and more sophisticated investigations, which deliver more detailed insights into the CuAAC’s catalytic cycle and the species involved. As diverging mechanistic views are presented in articles, books and online resources, we intend to present the research efforts in this field during the past decade and finally give an up-to-date picture of the currently accepted dinuclear mechanism of CuAAC. Additionally, we hope to inspire research efforts on the development of molecularly defined copper(I) catalysts with defined structural characteristics, whose main advantage in contrast to the regularly used precatalyst reagent mixtures is twofold: on the one hand, the characteristics of molecularly defined, well soluble catalysts can be tuned according to the particular requirements of the experiment; on the other hand, the understanding of the CuAAC reaction mechanism can be further advanced by kinetic studies and the isolation and characterization of key intermediates.

https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-9-308.pdf

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

Metallated molecular materials of fluorene derivatives and their analogues

Within the past years, several catalyst systems have been discovered that promote the carboxylation of terminal alkynes with formation of propiolic acids. This reaction concept is particularly topical in that it involves the functionalization of a C–H bond and the incorporation of CO2 into an organic molecule without need for strong bases or aggressive organometallic reagents. The present article reviews the development of this new reaction type and critically compares the reaction and catalyst concepts disclosed in the literature.

Catalytic C–H Carboxylation of Terminal Alkynes with Carbon Dioxide

Bicyclic and tricyclic bis(amido)cyclodiphosph(III)azane compounds of main group elements

Structural Variation in Silver Acetylide Complexes: Syntheses and X-ray Structure Determinations of [Ph3PAgC⋮CPh]4·3.5THF and [Me3PAgC⋮CSiMe3]∞

A New Method for the Synthesis of Heterometallic Complexes: Syntheses and Structures of [(PhCH2CH2NLi)3Sb(thf)]2 and [Sb3(cyN)4(NMe2)2]Li

Neue Methode zur Synthese von Heterometallkomplexen – Synthesen und Strukturen von [(PhCH2CH2NLi)3Sb(thf)]2 und [Sb3(cyN)4(NMe2)2]Li

Preparation of copper organometallics via nucleophilic substitution of CpCuPPh3: syntheses and x-ray structure determinations of [Li(THF)4]+[(fluorenyl)2CuPPh3]- and [Cy3PCu(.mu.-C.tplbond.CtBu)2Cu(PPh3)2] (THF = tetrahydrofuran, fluorenyl = C13H9)

Transmetalation reactions of the polyimido Sb(III) anions [Sb(3)(NCy)(4)(HNCy)(2)](-), [Sb(2)(NCy)(4)](2)(-), and [Sb(NCy)(3)](3)(-) with metal sources allows the logical assembly of cage compounds containing various mixed-metal stoichiometries. The breadth of this approach is illustrated by the syntheses of [Sb(NCy)(4)(HNCy)(2)]K.2(toluene) (1), containing an early main group metal, [Sb(2)(NCy)(4)](2)M(4) (M = Cu (2), Ag (3)), containing transition metals, and [Sb(NCy)(3)Pb(3)] (4), containing a p-block metal. The low-temperature X-ray structures of complexes 1-4 have been determined. Crystal data: 1, monoclinic, space group C2/c, a = 18.418(3) A, b = 11.457(2) A, c = 24.798(6) A, beta = 90.24(2) degrees, Z = 4; 3, triclinic, space group Po, a = 11.501(2) A, b = 13.752(3) A, c = 22.868(5) A, alpha = 103.50(3) degrees, beta = 95.89(3) degrees, gamma = 96.71(3) degrees, Z = 2; 4, triclinic, space group Po, a = 11.071(2) A, b = 14.892(2) A, c = 17.262(2) A, alpha = 65.36(3) degrees, beta = 74.21(3) degrees, gamma = 70.70(3) degrees, Z = 2. The structure of 2 has been reported in preliminary form. The K(+) ion of 1 is coordinated by four of the N centers of the [Sb(3)(NCy)(4)(HNCy)(2)](-) ligand. In addition, beta-C(-H).K interactions involving four of the Cy groups and MeC(-H).K interactions involving two toluene molecules give the K(+) ion a 10-coordinate geometry. In 2 and 3, the N centers of two [Sb(2)(NCy)(4)](2)(-) dianions symmetrically coordinate a central M(4) square-planar core. The symmetrical complexation of three Pb(II) centers by two [Sb(NCy)(3)](3)(-) trianions produces an 11-membered polyhedral cage structure in 4.

Assembly of Mixed-Metal Cages Using Polyimido Antimony(III) Anions. Syntheses and Structures of [Sb3(NCy)4(HNCy)2]K·2(toluene), [Sb2(NCy)4]2M4 (M = Cu, Ag), and [Sb(NCy)3]2Pb3 (Cy = Cyclohexyl, C6H11)

Moira-Ann Rennie

Papers

Structural Variation in Silver Acetylide Complexes: Syntheses and X-ray Structure Determinations of [Ph3PAgC⋮CPh]4·3.5THF and [Me3PAgC⋮CSiMe3]∞

A New Method for the Synthesis of Heterometallic Complexes: Syntheses and Structures of [(PhCH2CH2NLi)3Sb(thf)]2 and [Sb3(cyN)4(NMe2)2]Li

Neue Methode zur Synthese von Heterometallkomplexen – Synthesen und Strukturen von [(PhCH2CH2NLi)3Sb(thf)]2 und [Sb3(cyN)4(NMe2)2]Li

Preparation of copper organometallics via nucleophilic substitution of CpCuPPh3: syntheses and x-ray structure determinations of [Li(THF)4]+[(fluorenyl)2CuPPh3]- and [Cy3PCu(.mu.-C.tplbond.CtBu)2Cu(PPh3)2] (THF = tetrahydrofuran, fluorenyl = C13H9)

Assembly of Mixed-Metal Cages Using Polyimido Antimony(III) Anions. Syntheses and Structures of [Sb3(NCy)4(HNCy)2]K·2(toluene), [Sb2(NCy)4]2M4 (M = Cu, Ag), and [Sb(NCy)3]2Pb3 (Cy = Cyclohexyl, C6H11)