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XB₂Bi₂ (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

ABSTRACT: Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi-B-B-Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculations reveal that these ptSi/Ge/Sn/Pb species are the global minima on their potential energy surfaces. Born-Oppenheimer molecular dynamics (BOMD) simulations indicate that XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters are robust. Bonding analyses indicate that 20 VEs are perfect for the ptX XB₂Bi₂ (X = Si, Ge, Sn, Pb): two lone pairs of Bi atoms; one 5c-2e π, and three σ bonds (two Bi-X 2c-2e and one B-X-B 3c-2e bonds) between the ligands and X atom; three 2c-2e σ bonds and one delocalized 4c-2e π bond between the ligands. The ptSi/Ge/Sn/Pb XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters possess 2π/2σ double aromaticity, according to the (4n + 2) Hückel rule.

SUBMITTER: Jin YX

PROVIDER: S-EPMC10931956 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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XB2Bi2 (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

Jin Yan-Xia YX Guo Jin-Chang JC

International journal of molecular sciences 20240229 5

Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi-B-B-Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculati ...[more]

PMID: 38474066

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Project description:In a reaction of tantalocene trihydride with the low valent aryl tin cation [Ar*Sn(C6H6)][Al(OC{CF3}3)4] (1a) the hydridostannylene complex [Cp2TaH2-Sn(H)Ar*][Al(OC{CF3}3)4] (2) was synthesized. Hydride bridged adducts [Cp2WH2EAr*][Al(OC{CF3}3)4] (E = Sn 3a, Pb 3b) were isolated as products of the reaction between Cp2WH2 and cations [Ar*E(C6H6)][Al(OC{CF3}3)4] (E = Sn 1a, Pb 1b). The tin adduct 3a exhibits a proton migration to give the hydridostannylene complex [Cp2W(H)[double bond, length as m-dash]Sn(H)Ar*][Al(OC{CF3}3)4] 4a. The cationic complex 4a is deprotonated at the tin atom in reaction with base MeNHC at 80 °C to give a hydrido-tungstenostannylene [Cp2W(H)SnAr*] 5a. Reprotonation of metallostannylene 5a with acid [H(Et2O)2][BArF] provides an alternative route to hydridotetrylene coordination. Complex 4a adds hydride to give the dihydrostannyl complex [Cp2W(H)-SnH2Ar*] (7). With styrene 4a shows formation of a hydrostannylation product [Cp2W(H)[double bond, length as m-dash]Sn(CH2CH2Ph)Ar*][Al(OC{CF3}3)4] (8). The lead adduct 3b was deprotonated with MeNHC to give plumbylene 5b [Cp2W(H)PbAr*]. Protonation of 5b with [H(Et2O)2][Al(OC{CF3}3)4] at -40 °C followed by low temperature NMR spectroscopy indicates a hydridoplumbylene intermediate [Cp2W(H)[double bond, length as m-dash]Pb(H)Ar*]+ (4b). Hydrido-tungstenotetrylenes of elements Ge (5c), Sn (5a) and Pb (5b) were also synthesized reacting the salt [Cp2W(H)Li]4 with organotetrylene halides. The metallogermylene [Cp2W(H)GeAr*] (5c) shows an isomerization via 1,2-H-migration to give the hydridogermylene [Cp2W[double bond, length as m-dash]Ge(H)Ar*] (9), which is accelerated by addition of AIBN. 9 is at rt photochemically transferred back to 5c under light of a mercury vapor lamp. Zirconocene dihydride [Cp2ZrH2]2 reacts with tin cation 1a to give the trinuclear hydridostannylene adduct 10 [({Cp2Zr}2{μ-H})(μ-H)2μ-Sn(H)Ar*][Al(OC{CF3}3)4]. Deprotonation of 10 was carried out using benzyl potassium to give neutral [({Cp2Zr}2{μ-H})(μ-H)μ-Sn(H)Ar*] (11). 11 was also obtained from the reaction of low valent tin hydride [Ar*SnH]2 with two equivalents of [Cp2ZrH2]2. The trihydride Ar*SnH3 reacts with half of an equivalent of [Cp2ZrH2]2 under evolution of hydrogen and formation of a dihydrostannyl complex 13 [Cp2Zr(μ-H)SnH2Ar*]2 and with further equivalents of Ar*SnH3 to give bis(hydridostannylene) complex [Cp2Zr{Sn(H)Ar*}2].

Dataset Information

XB₂Bi₂ (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

Publications

XB<sub>2</sub>Bi<sub>2</sub> (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

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