Issue 14, 2022

Hydridotetrylene [Ar*EH] (E = Ge, Sn, Pb) coordination at tantalum, tungsten, and zirconium

Abstract

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].

Graphical abstract: Hydridotetrylene [Ar*EH] (E = Ge, Sn, Pb) coordination at tantalum, tungsten, and zirconium

Supplementary files

Article information

Article type
Edge Article
Submitted
17 yan 2022
Accepted
21 fev 2022
First published
22 fev 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 3999-4009

Hydridotetrylene [Ar*EH] (E = Ge, Sn, Pb) coordination at tantalum, tungsten, and zirconium

M. Widemann, S. Jeggle, M. Auer, K. Eichele, H. Schubert, C. P. Sindlinger and L. Wesemann, Chem. Sci., 2022, 13, 3999 DOI: 10.1039/D2SC00297C

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