Copper(I) Alkyne and Alkynide Complexes

Abstract

The synthesis, structure, bonding motifs, reaction chemistry, and some potential applications of copper(I) alkyne and alkynide compounds as well as current trends in this field of chemistry are reported.

High‐Nuclear Organometallic Copper(I)–Alkynide Clusters: Thermochromic Near‐Infrared Luminescence and Solution Stability

“…As shown in Figure 1a,t his neutralc luster is protected by ten tBuCC À and five CF 3 COO À ions and furtherc onsolidated by numerous inner close Cu···Cu contacts, which fall in the range of 2.4668(16)-2.7993(8) ,a ss een in many other Cu I clusters. [17] Structure of [Cu 16 (tBuCC) 12 (CF 3 COO) 4 [15] Although recent theoretical calculations [16] indicated the energy of cupro- 5 ] cluster by omitting guesttBuCCH molecule.…”

Synthesis, Structure, and Reactivity of Niobium and Tantalum Alkyne Complexes

“…The ease with which these compounds can be synthesized, as well as the variety of different alkyne substrates supported, make them ideal starting materials for group 5 Prior to the advent of these conveniently accessible Nb (15) and Ta (16) alkyne trihalide starting materials, the syntheses of most group 5 alkyne complexes typically involved the reduction of a high-valent M V or M IV organometallic precursor that already contained a stabilizing ancillary ligand, such as a cyclopentadienyl (Cp = C 5 H 5 ) unit. Although there are some examples of M III compounds that are stable enough to be isolated and characterized (e.g., 22, 28, 33; vide infra), in most cases the reduced M III species was generated in situ and immediately treated with an alkyne substrate to afford the desired M V alkyne organometallic complex.…”

Alkynyl Coinage Metal Clusters and Complexes–Syntheses, Structures, and Strategies

“…[138] Ah oneycomb heterometallic aggregate constructed from hexagonal motifs similar to the one seen in cluster 91 was reported by Blanco and co-workers. The gold phosphine alkynide [Au(CCPh)PPh 3 ]w as reactedw ith AgOTff orming the highly ordered cluster[ Ag 12 Au 10 (CCPh) 17 (OTf) 5 (PPh 3 ) 3 ]( 92). Interestingly,s mall variations of the silver salt, that is, using Ag(OTf)(tht) led to the formation of highern uclearity of the resulting cluster [Ag 26 Au 20 (CCPh) 34 (OTf) 12 (PPh 3 ) 6 (tht) 2 ]( 93)i ncorporating the "tht" co-ligand.…”

“…In addition to that, the h 2 side-on coordination to the triple bond plays ap rominent role in these coordination compounds. [15][16][17] Both modes are observed in different combinations giving rise to variousa lkynyl coordinationsr anging from m 2 to m 4 -bridging ligands (Figure 1). Both the bulkiness of the alkyne substituent, as well as the variable coordination modes kinetically stabilize many different metal clusters of different shapes and compositions.…”