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An isolable, crystalline complex of square-planar silicon(IV).

ABSTRACT: The structure and reactivity of silicon(IV), the second most abundant element in our Earth's crust, is determined by its invariant tetrahedral coordination geometry. Silicon(IV) with a square-planar configuration (ptSi ^IV ) represents a transition state. Quantum theory supported the feasibility of stabilizing ptSi ^IV by structural constraint, but its isolation has not been achieved yet. Here, we present the synthesis and full characterization of the first square-planar coordinated silicon(IV). The planarity provokes an extremely low-lying unoccupied molecular orbital that induces unusual silicon redox chemistry and CH-agostic interactions. The small separation of the frontier molecular orbitals enables visible-light ligand-element charge transfer and bond-activation reactivity. Previously, such characteristics have been reserved for d-block metals or low-valent p-block elements. Planarization transfers them, for the first time, to a p-block element in the normal valence state.

SUBMITTER: Ebner F

PROVIDER: S-EPMC8367297 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Among Earth-abundant catalyst systems, iron-carbene intermediates that perform C-C bond forming reactions such as cyclopropanation of olefins and C-H functionalization via carbene insertion are rare. Detailed descriptions of the possible electronic structures for iron-carbene bonds are imperative to obtain better mechanistic insights and enable rational catalyst design. Here, we report the first square-planar iron-carbene complex (MesPDPPh)Fe(CPh2), where [MesPDPPh]2- is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. The compound was prepared via reaction of the disubstituted diazoalkane N2CPh2 with (MesPDPPh)Fe(thf) and represents a rare example of a structurally characterized, paramagnetic iron-carbene complex. Temperature-dependent magnetic susceptibility measurements and applied-field Mössbauer spectroscopic studies revealed an orbitally near-degenerate S = 1 ground state with large unquenched orbital angular momentum resulting in high magnetic anisotropy. Spin-Hamiltonian analysis indicated that this S = 1 spin system has uniaxial magnetic properties arising from a ground MS = ±1 non-Kramers doublet that is well-separated from the MS = 0 sublevel due to very large axial zero-field splitting (D = -195 cm-1, E/D = 0.02 estimated from magnetic susceptibility data). This remarkable electronic structure gives rise to a very large, positive magnetic hyperfine field of more than +60 T for the 57Fe nucleus along the easy magnetization axis observed by Mössbauer spectroscopy. Computational analysis with complete active space self-consistent field (CASSCF) calculations provides a detailed electronic structure analysis and confirms that (MesPDPPh)Fe(CPh2) exhibits a multiconfigurational ground state. The majority contribution originates from a configuration best described as a singlet carbene coordinated to an intermediate-spin FeII center with a (dxy)2{(dxz),(dz2)}3(dyz)1(dx2-y2)0 configuration featuring near-degenerate dxz and dz2 orbitals.

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An isolable, crystalline complex of square-planar silicon(IV).

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