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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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50

Citations

90

References

2021

Year

Max Widemann, Klaus Eichele, Hartmut Schubert, Christian P. Sindlinger, Steffen Klenner, Rainer Pöttgen, Lars Wesemann
Angewandte Chemie International Edition

Abstract

Tetrylidynes [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)Rh≡SnAr*] (10) and [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)Rh≡PbAr*] (11) are accessed for the first time via dehydrogenation of dihydrides [(Ph<sub>3</sub> P)<sub>2</sub> RhH<sub>2</sub> SnAr*] (3) and [(Ph<sub>3</sub> P)<sub>2</sub> RhH<sub>2</sub> PbAr*] (7) (Ar*=2,6-Trip<sub>2</sub> C<sub>6</sub> H<sub>3</sub> , Trip=2,4,6-triisopropylphenyl), respectively. Tin dihydride 3 was either synthesized in reaction of the dihydridostannate [Ar*SnH<sub>2</sub> ]<sup>-</sup> with [(Ph<sub>3</sub> P)<sub>3</sub> RhCl] or via reaction between hydrides [(Ph<sub>3</sub> P)<sub>3</sub> RhH] and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>1</mml:mn> <mml:mo>/</mml:mo> <mml:mn>2</mml:mn></mml:mrow> </mml:math> [(Ar*SnH)<sub>2</sub> ]. Homologous lead hydride [(Ph<sub>3</sub> P)<sub>2</sub> RhH<sub>2</sub> PbAr*] (7) was synthesized analogously from [(Ph<sub>3</sub> P)<sub>3</sub> RhH] and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>1</mml:mn> <mml:mo>/</mml:mo> <mml:mn>2</mml:mn></mml:mrow> </mml:math> [(Ar*PbH)<sub>2</sub> ]. Abstraction of hydrogen from 3 and 7 supported by styrene and trimethylphosphine addition yields tetrylidynes 10 and 11. Stannylidyne 10 was also characterized by <sup>119</sup> Sn Mössbauer spectroscopy. Hydrogenation of the triple bonds at room temperature with excess H<sub>2</sub> gives the cis-dihydride [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)RhH<sub>2</sub> PbAr*] (12) and the tetrahydride [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)RhH<sub>2</sub> SnH<sub>2</sub> Ar*] (14). Complex 14 eliminates spontaneously one equivalent of hydrogen at room temperature to give the dihydride [(Me<sub>3</sub> P)<sub>2</sub> (Ph<sub>3</sub> P)RhH<sub>2</sub> SnAr*] (13). Hydrogen addition and elimination at stannylene tin between complexes 13 and 14 is a reversible reaction at room temperature.

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