Dataset Information

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me₃ P)₂ (Ph₃ P)Rh≡E-Ar*] (E=Sn, Pb).

ABSTRACT: Tetrylidynes [(Me₃ P)₂ (Ph₃ P)Rh≡SnAr*] (10) and [(Me₃ P)₂ (Ph₃ P)Rh≡PbAr*] (11) are accessed for the first time via dehydrogenation of dihydrides [(Ph₃ P)₂ RhH₂ SnAr*] (3) and [(Ph₃ P)₂ RhH₂ PbAr*] (7) (Ar*=2,6-Trip₂ C₆ H₃ , Trip=2,4,6-triisopropylphenyl), respectively. Tin dihydride 3 was either synthesized in reaction of the dihydridostannate [Ar*SnH₂ ]^- with [(Ph₃ P)₃ RhCl] or via reaction between hydrides [(Ph₃ P)₃ RhH] and 1/2 [(Ar*SnH)₂ ]. Homologous lead hydride [(Ph₃ P)₂ RhH₂ PbAr*] (7) was synthesized analogously from [(Ph₃ P)₃ RhH] and 1/2 [(Ar*PbH)₂ ]. Abstraction of hydrogen from 3 and 7 supported by styrene and trimethylphosphine addition yields tetrylidynes 10 and 11. Stannylidyne 10 was also characterized by ¹¹⁹ Sn Mössbauer spectroscopy. Hydrogenation of the triple bonds at room temperature with excess H₂ gives the cis-dihydride [(Me₃ P)₂ (Ph₃ P)RhH₂ PbAr*] (12) and the tetrahydride [(Me₃ P)₂ (Ph₃ P)RhH₂ SnH₂ Ar*] (14). Complex 14 eliminates spontaneously one equivalent of hydrogen at room temperature to give the dihydride [(Me₃ P)₂ (Ph₃ P)RhH₂ SnAr*] (13). Hydrogen addition and elimination at stannylene tin between complexes 13 and 14 is a reversible reaction at room temperature.

SUBMITTER: Widemann M

PROVIDER: S-EPMC7986155 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Publications

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me3 P)2 (Ph3 P)Rh≡E-Ar*] (E=Sn, Pb).

Widemann Max M Eichele Klaus K Schubert Hartmut H Sindlinger Christian P CP Klenner Steffen S Pöttgen Rainer R Wesemann Lars L

Angewandte Chemie (International ed. in English) 20210201 11

Tetrylidynes [(Me3 P)2 (Ph3 P)Rh≡SnAr*] (10) and [(Me3 P)2 (Ph3 P)Rh≡PbAr*] (11) are accessed for the first time via dehydrogenation of dihydrides [(Ph3 P)2 RhH2 SnAr*] (3) and [(Ph3 P)2 RhH2 PbAr*] (7) (Ar*=2,6-Trip2 C6 H3 , Trip=2,4,6-triisopropylphenyl), respectively. Tin dihydride 3 was either synthesized in reaction of the dihyd ...[more]

PMID: 33438371

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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

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me₃ P)₂ (Ph₃ P)Rh≡E-Ar*] (E=Sn, Pb).

Publications

Synthesis and Hydrogenation of Heavy Homologues of Rhodium Carbynes: [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)Rh≡E-Ar*] (E=Sn, Pb).

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