Silver(I) complexes with substituted derivatives of the boron cluster anions as ligands

Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)

“…Silver(I) complex [Ag(CH 3 CN) 3 ] 2 [Ag 2 [2-B 10 H 9 F] 2 ] [64] with the monofluoro-substituted derivative of the closo-decaborate anion was isolated by the reaction between tetraphenylphosphonium 2-fluoro-closo-decaborate [2-B 10 H 9 F] 2and silver trifluoroacetate. The structure of this complex (Figure 2) is built of anions [Ag 2 [2- Cl]] [65] with triphenylphosphine Ph 3 P was also obtained for the monochloro-substituted derivative of the closo-dodecaborate anion. The binuclear complex was isolated when the [B 10 H 11 Cl] 2anions reacted with [Ag(Ph 3 P) 3 NO 3 ] in CH 3 CN or DMF.…”

“…The compound is a centrosymmetric complex in which the silver atoms coordinate the closo-dodecaborate anion along opposite edges (Ag-B 2.779 and 2.790 Å) that are as far as possible from the chlorine atom introduced (Figure 3). Silver(I) complex [Ag2(Ph3P)4[B12H11Cl]] [65] with triphenylphosphine Ph3P was also obtained for the monochloro-substituted derivative of the closo-dodecaborate anion. The binuclear complex was isolated when the [B10H11Cl] 2-anions reacted with [Ag(Ph3P)3NO3] in CH3CN or DMF.…”

“…For both the [B10H10] 2-and [B12H12] 2-anions, nickel(II) resulted in complex salts, whereas silver(I) afforded complexes with boron clusters coordinated by edges located as far as possible from the substituent introduced. Silver(I) complex [Ag2(Ph3P)4[B12H11Cl]] [65] with triphenylphosphine Ph3P was also obtained for the monochloro-substituted derivative of the closo-dodecaborate anion. The binuclear complex was isolated when the [B10H11Cl] 2-anions reacted with [Ag(Ph3P)3NO3] in CH3CN or DMF.…”

“…The introduction of cyclic ether molecules as an exo-polyhedral substituent into the boron cluster results in reduction of the total charge of the derivatives of the closo-decaborate anion. Thus, the reaction of salts of the undecahydrodecaborate anion [B 10 H 11 ]with 1,4-dioxane and tetrahydropyran gives derivatives of the closo-decaborate anion containing the organic molecules as substituents in position B( 2 In both complexes, silver coordinates four molecules of Ph 3 P forming cationic complex [Ag(PPh 3 ) 4 ] + [65], while the substituted derivative plays the role of a counterion. Both compounds are additional evidence that the silver(I) atom tends to form salts with monocharged derivatives of the boron clusters instead of forming complexes with them.…”

Recent Advances in the Synthesis of Polyamine Derivatives and Their Applications

“…Derivatives of this type react with neutral and negatively charged nucleophiles to form compounds with a functional group separated from the cluster by alkoxy spacer (side functional group). Derivatives of closo-borate anions with oxonium-type substituents can act as starting compounds for further modification, owing to opening reactions of cyclic substituents, which makes it possible to introduce biologically active groups into the boron cluster [75][76][77].…”