Na/Cu^II/Cu^I Complexes of Compartmental Schiff Base Ligands Incorporating the [Cu(NCO)₂]⁻ Ion

Abstract

Two new NaI/CuI,II polynuclear compounds [(NaCu3((R,R)‐3‐MeOSalcy)2(NCO)2](1) and [(NaCu2(3‐MeOSalpn)(NCO)2] (2) have been synthesized using the Schiff base (SB) ligands, (R,R)‐3‐MeOSalcy=(R,R)–N,N′‐bis(3‐methoxysalicylidene)‐1,2‐diaminocyclohexane and 3‐MeOSalpn=N,N′‐bis(3‐methoxysalicylidene)‐1,3‐diaminopropane, respectively. Both complexes contain the rarely observed linear [Cu(NCO)2]− ion which links [{CuII(SB)}2Na]+ ions in 1 or [{CuII(SB)Na}2]2+ ions in 2 producing different linear chain topologies. The mixed valent CuI/IINa network in compound 1 allows for greater magnetic isolation of the paramagnetic ions as compared to compound 2, leading to differences in their EPR spectra.

Isocyanide Cu(I) complexes with unexpected μ2‐bridging pseudohalides: Synthesis, characterization and catalytic activity towards CuAAC

“…As far as we know, these are the only two Cu(I) complexes reported where the pseudohalide is μ 2 ‐bridging to the metal centre. In all the other structures described in the literature, the pseudohalides are terminal and coordinated exclusively to one Cu(I) 33,46,47,50–57 . In particular, the geometry of Cu‐NCO illustrated in Figure 2 shows each Cu(I) atom coordinated to two CNXyl ligands and one OCN − group, which generates a centrosymmetric dimer by a long contact between the N atom and a nearby molecule with concerted unsymmetrical two nitrogen bridges (Cu(1)‐N(3) of 2.071(2) and 2.122(2) Å).…”

“…In all the other structures described in the literature, the pseudohalides are terminal and coordinated exclusively to one Cu(I). 33,46,47,[50][51][52][53][54][55][56][57] In particular, the geometry of Cu-NCO illustrated in Figure 2 shows each Cu(I) atom coordinated to two CNXyl ligands and one OCN À group, which generates a centrosymmetric dimer by a long contact between the N atom and a nearby molecule with concerted unsymmetrical two nitrogen bridges (Cu(1)-N(3) of 2.071(2) and 2.122(2) Å). The angle N(3)-Cu(1)-N(3 0 ) of 92.31(9) places both OCN À groups in apical positions, displaced by 1.509 Å from the basal plane, which is delimited by the two tetrahedral copper ions and the isocyanide ligands.…”