Amidinato– and Guanidinato–Cobalt(I) Complexes: Characterization of Exceptionally Short Co–Co Interactions

Abstract

CoCo loco! Ligand‐bridged dimers (see picture) with the shortest known Co–Co interactions are the first amidinato and guanidinato cobalt(I) complexes. The nature of the interactions has been probed by magnetic and theoretical investigations, and has been shown to be multiconfigurational. Preliminary reactivity studies of the complexes have also been carried out.

[Co2@Ge16]4−: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

“…The title clusters [Co 2 @Ge 16 ] 4À were obtained by ar eactiono f [{(ArN) 2 CtBu}Co(h 6 -toluene)] (Ar = 2,6-diisopropylphenyl) [22] and K 4 Ge 9 in the presence of 2,2,2-crypt in ethylenediamine (en). Monitoring the reaction solution by ESI-MS reveals that there are several cluster-containing products present in solution (Figure S6 in the Supporting Information).…”

Trapping of an NiII Sulfide by a CoI Fulvene Complex

“…5,6 A number of late transition metal carbene (CR 2 2-), nitrene (NR 2-), nitride (N 3-), and phosphinidene (PR 2-) complexes have also been reported in recent years. [7][8][9][10][11][12][13][14][15][16][17][18] While a few of these complexes have been isolated, they tend to be extremely reactive, and often can only be observed spectroscopically. [19][20][21][22] Nonetheless, it is clear that synthetic chemists are now beginning to identify the combination of ligand requirements and synthetic procedures that can successfully generate late-metal ligand multiple bonds.…”

Reactivity of Paramagnetic FeII–Bis(amidinate) Complexes

“…Carbonyl insertion is relatively common for Fe and Co amidinates with bulky substituents. [16,18,19] The regiochemistry seems to be determined by steric factors as insertion usually occurs next to the nitrogen that carries the most sterically demanding substituent. [17] Attempts to characterise the red intermediate {presumably the bis-CO adduct [( DippPh L) 2 Fe(CO) 2 ]} were unsuccessful.…”