The 12-ethynylmonocarba-closo-dodecaborate anion as a versatile ligand for Cu(i) alkyne and heterobimetallic Cu(i)/M(ii) (M = Pd, Pt) alkynide complexes

Abstract

The anionic 12-ethynyl-monocarba-closo-dodecaborate cluster is employed as a ligand for the preparation of Cu(i) and heterobimetallic Cu(i)/Pd(ii) or Cu(i)/Pt(ii) complexes.

Silver(I) Clusters Stabilized by the Carba‐closo‐dodecaboranylethynyl Ligand with O‐Donor Coligands and Template Ions

“…Especially, the coordination chemistry of the 12‐ethynylcarba‐ closo ‐dodecaborate ion [12‐HC≡C‐ closo ‐1‐CB 11 H 11 ] – and the respective ethynido ligand {12‐C≡C‐ closo ‐1‐CB 11 H 11 } 2– (Figure ) was studied in recent years. Salts of the [12‐HC≡C‐ closo ‐1‐CB 11 H 11 ] – ion are, similar to other alkynyl‐functionalized { closo ‐1‐CB 11 } derivatives, accessible from the respective iodinated { closo ‐1‐CB 11 } cluster via a Pd‐catalyzed cross‐coupling reaction,, The dianion {12‐C≡C‐ closo ‐1‐CB 11 H 11 } 2– was employed as ligand in coinage metal coordination chemistry of gold(I),, silver(I) (Figure ),, , and more recently, copper(I) , . In addition, first palladium(II) and platinum(II) complexes have been reported .…”

“…[7] More often, the {closo-1-CB 11 } cluster is bonded to a functional group that binds to the metal. Phosphanes, [9] nitriles, [10] N-heterocyclic carbenes, [11] and alkynes [12][13][14][15][16][17][18] with carba-closo-dodecaboranyl groups are recent examples for such derivatives.…”

“…Salts of the [12-HCϵC-closo-1-CB 11 H 11 ]ion are, similar to other alkynyl-functionalized {closo-1-CB 11 } derivatives, accessible from the respective iodinated {closo-1-CB 11 } cluster via a Pdcatalyzed cross-coupling reaction, [19,20] The dianion {12-CϵC-closo-1-CB 11 H 11 } 2was employed as ligand in coinage metal coordination chemistry of gold(I), [12,16] silver(I) (Figure 1), [13,15,16] and more recently, copper(I). [17,18] In addition, first palladium(II) and platinum(II) complexes have been reported. [18] The electronic and structural properties of the {12-CϵC-closo-1-CB 11 H 11 } 2ligand are decisively determined by the spherical and anionic {closo-1-CB 11 } cage, which is bonded via boron to the CϵC moiety.…”

“…[17,18] In addition, first palladium(II) and platinum(II) complexes have been reported. [18] The electronic and structural properties of the {12-CϵC-closo-1-CB 11 H 11 } 2ligand are decisively determined by the spherical and anionic {closo-1-CB 11 } cage, which is bonded via boron to the CϵC moiety. Unprecedented coordi- (4-MePy = 4-CH 3 C 5 H 4 N).…”

Sonogashira coupling of the ethynyl monocarborane [CB11H11-12-CCH]−

“…They can be used to form side-on mononuclear metal complexes with Cu(I) and Ag(I) (Fig. 2b), 33,34 but they also enable formation of structurally versatile, highly luminescent multinuclear assemblies with sideon as well as end-on metal interactions with Cu(I), Ag(I), and Au(I). [35][36][37][38][39][40] Additionally, electronic effects and electrochemical trends in alkynyl monocarboranes were studied.…”