Three types of oxime species, i.e.,
4-morpholylcarbamidoxime
(hydroxyguanidine), phenylacetamidoxime and benzamidoxime
(amidoximes), and cyclohexanone oxime and benzophenone
oxime (ketoximes), react at room temperature with the 2-nitrilium closo-decaborate clusters, leading to 2-iminium closo-decaborates (14 examples; 57–94%). These species
were characterized by ICPMS-based boron elemental analysis, HRESI–-MS, molar conductivity, IR, 1H{11B}, and 11B{1H} NMR spectroscopies, and additionally
by single-crystal X-ray diffraction (for six compounds). On the basis
of kinetic data, ΔH
⧧, ΔS
⧧, and ΔG
⧧ of the additions were determined, showing a 4 order-of-magnitude
decrease in reactivity from the hydroxyguanidine to the aromatic
ketoxime as entering nucleophiles. The results of DFT calculations
indicate that the mechanism for these reactions is stepwise and is
realized through the formation of the orientation complex of the nitrone
form, R2R3CN+(H)O–, of oximes with [B10H9NCEt]−, giving further an acyclic intermediate (the rate-determining
step), followed by proton migration, leading to the addition product.
The calculated overall activation barrier for these transformations
is consistent with the experimental kinetic observations. This work
provides, for the first time, a broad nucleophilicity series of oximes,
which is useful to control various nucleophilic additions of oxime
species.
Three types of N(H)-nucleophiles were used to study the nucleophilic addition to the CN group of the 2-propanenitrilium closo-decaborate cluster giving N-closo-decaborato amidrazones.
Multinuclear complexes or clusters are rarely investigated in medicinal inorganic chemistry although they represent structural intermediates between molecules and nanomaterials. We present in this report two strategies towards Tc-containing clusters. In a pre-assembly approach, the preformed but incomplete cluster fragment [Re (μ -OH) (μ -OH)(CO) ] reacts with [ Tc(CO) ] to the highly stable [ TcRe (μ -OH) (CO) ] cube. The same structure self-assembles when reacting the mononuclear Re and Tc precursors in one pot. Integrating the coordinating OH groups from Schiff bases in this concept leads straight to dinuclear, mixed-metal complexes of the type [ TcRe(μ -O^N-R ) (CO) ] in quantitative yields. Both strategies are unprecedented and open a future path towards clusters, incorporating a Tc radiolabel while being decorated with targeting or cytotoxic moieties.
The self-exchange kinetics of CO ligands in the solvated forms of the commonly used complex [MBr3(CO)3](2-) (M = Re, (99)Tc) were investigated in-depth by (13)C NMR spectroscopy in organic solvents such as dimethylformamide and methanol. The two homologues exhibit surprisingly different chemical behavior. In the case of rhenium, the stable intermediate [NEt4][ReBr2(CO)4] was isolated and characterized by (13)C NMR and IR spectroscopy as well as by single-crystal X-ray diffraction. For technetium, no such intermediate could be identified. The activation parameters (ΔH(⧧) = 110 ± 7 kJ mol(-1) and ΔS(⧧) = 127 ± 22 J mol(-1) K(-1)) and the observed influences of different ligands and solvents suggest a dissociative-interchange-type mechanism with a second-order rate constant for the formation of [NEt4][ReBr2(CO)4], k1 = 0.039 ± 0.001 M(-1) s(-1) at 274 K. On the basis of variable-temperature NMR experiments, kinetic simulations, and density functional theory calculations, a complete model for the CO self-exchange, including all respective rate constants, is reported.
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