Ligand protonated IrI bisphosphine carbonyl complexes isolated as halide salts equilibrate with their neutral IrIII–H congeners in solution. The equilibrium constant and energy barrier to interconversion are dependent on the identity of the halide.
A group of symmetrically‐trisubstituted‐1,3,5‐triazine‐based molecules have been studied extensively in order to create Piedfort pairs that are intended to be employed in sequestration of small molecules. Extensive inter and intramolecular interactions observed in the solid‐state of the studied triazine molecules lead to the formation of one‐dimensional ribbon and two‐dimensional sheet motifs. Koneramine formation was applied as a new strategy to increase the bulkiness of the substituents on 1,3,5‐triazine ring that prevented the formation of ribbons and sheets yet yielded hydrogen‐bonded dimer. The protonated forms of one of the triazine compound showed that the triazine ring nitrogens are more basic than amine nitrogens on the periphery; protonated N2,N4,N6‐triphenyl‐1,3,5‐triazine‐2,4,6‐triamine resulted in eccentric Piedfort pairs that displayed aesthetic structural patterns possessing variety of inter and intramolecular interactions including stacking between electron deficient triazine ring of one member and electron rich aryl ring of another member.
By
employing a simple strategy of reacting SO2 gas with
easily attainable hydride donors such as 2-substituted-1,3-dimethyl-2,3-dihydro-1H-benzo[d]imidazole, benzimidazoline and
SO2 were converted into benzimidazolium bisulfate at room
temperature and atmospheric pressure. Bisulfate originated from SO2 and hydride from benzimidazoline and aerial oxygen. Metastable
dimers of bisulfate anions were observed in the solid state and in
solution where the anions are not stabilized by encapsulation in cages
but through hydrogen bonding from benzimidazolium cations. All three
benzimidazolines and resulted benzimidazolium bisulfates have been
characterized using 1H and 13C NMR spectroscopy,
high-resolution electrospray ionization mass spectrometry, and single
crystal X-ray diffraction techniques.
A series of low-valent square-planar Rh complexes [
LH
Rh][X] (X = PF6, Br, Cl, I) bearing two protic imidazolyl phosphines (one
κ2) and a CO ligand were synthesized and fully characterized.
A comparison of the CO stretching frequencies with those of the previously
reported [
LH
Ir][X] complexes indicates a much lower electron density at the Rh centers.
This lower electron density at Rh results in a lower propensity to
undergo ligand to metal proton transfer, and in contrast to observations
with Ir, the [
LH
Rh][X] complexes (X = Cl, Br, I) do not equilibrate with their metal-protonated
congeners. Furthermore, the weaker bond strengths of Rh complexes
compared to Ir lead to an increased degree of fluxionality in the
former, along with a difference in reactivity with hydrogen (H2) and iodine (I2).
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