Open-shell doublet character in a hexaazatrinaphthylene trianion complex.
نویسندگان
چکیده
Three-electron reduction of hexaazatrinaphthylene (HAN) with a magnesium(I) reagent leads to [(HAN){Mg(nacnac)}3] (1), containing a [HAN](3-) ligand with a spin of S = 1/2. Ab initio calculations reveal that the [HAN](3-) ligand in 1 has a ground-state wave function with multiconfigurational properties, and can be described as a triradicaloid species with a small amount of open-shell doublet character.
منابع مشابه
5-Dehydro-1,3-quinodimethane: a hydrocarbon with an open-shell doublet ground state.
electrons, that is, an “open-shell doublet.” Although low-spin, open-shell states occur in molecules containing transition metals, the ground states of organic molecules are rarely of this type. Organic biradicals can have open-shell singlet ground states, depending on the orbital structure, but DMX is the first example of an organic triradical with an open-shell doublet ground state. Qualitati...
متن کاملElectronic structures of Group 9 metallocorroles with axial ammines.
The electronic structures of metallocorroles (tpfc)M(NH(3))(2) and (tfc)M(NH(3))(2) (tpfc is the trianion of 5,10,15-(tris)pentafluorophenylcorrole, tfc is the trianion of 5,10,15-trifluorocorrole, and M = Co, Rh, Ir) have been computed using first principles quantum mechanics [B3LYP flavor of Density Functional Theory (DFT) with Poisson-Boltzmann continuum solvation]. The geometry was optimize...
متن کاملSinglet open-shell character of conjugated Kekulé molecules
We have studied the properties of singlet open-shell molecules that are designed, synthesized, and isolated by us. The molecules contain p-quinodimethane or cumulene structures in the middle of their skeletons, and also equip spindelocalizing moieties, phenalenyl, in the both ends for thermodynamic stabilization. Crystal structures and electronic spectra revealed that these conjugated Kekulé mo...
متن کاملOpen-shell singlet character of stable derivatives of nonacene, hexacene and teranthene.
The electronic ground states of the recently synthesized stable nonacene derivatives (J. Am. Chem. Soc. 2010, 132, 1261) are open-shell singlets with a polyradical nature instead of closed-shell singlets as originally assumed, according to the unrestricted broken spin-symmetry density functional theory (UBS-DFT) computations (at B3LYP/6-31G*). It is the bulky protecting groups, not the transfer...
متن کاملCa-Ca interaction in inverse sandwich Ca-C8H8-Ca.
The inverse sandwich Ca-C8H8-Ca is predicted to be an open-shell singlet state. Since the C8H8 ligand prevents the spin-up and spin-down electrons of different calcium atoms from forming Ca-Ca bonds, the spin-coupling electrons lead to a singlet diradical character. The metal-ligand interaction contributes to the stability of Ca-C8H8-Ca against dissociation and isomerization. For the coordinati...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 51 57 شماره
صفحات -
تاریخ انتشار 2015