4.7 Article

Insertion of CS2 into a Phosphorus-Arsenic Single Bond and Investigations on Phosphane Arsanyldithiocarboxylates

Journal

INORGANIC CHEMISTRY
Volume 60, Issue 15, Pages 11591-11598

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c01569

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Funding

  1. Fonds der Chemischen Industrie
  2. Studienstiftung des Deutschen Volkes

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The synthesis and reactivity of sterically demanding phosphaarsanes were described in this study, with a new structural motif phosphane arsanyldithiocarboxylate being discovered. An alternative synthetic route was reported to enable access to a wider range of phosphane arsanyldithiocarboxylates. The interpnictogen dithiocarboxylates showed an interesting bonding situation with significantly elongated As-S bond due to negative hyperconjugation within the molecule.
The synthesis and reactivity of sterically demanding phosphaarsanes TerR(1)P-AsR2 (3) is described. These species were selectively synthesized via metathesis reactions of Terstabilized [Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl] potassium phosphides TerR(1)PK (1) with the N-heterocyclic chloroarsane ClAs{N(tBu)CH2}(2) (2). Conversion of the n-butyl-substituted phosphaarsane 3c with the reactive heterocumulene CS2 leads to an insertion into the P-As bond, yielding the phosphane arsanyldithiocarboxylate TerR(1)P-C(S)S-AsR2 (4c) as a new structural motif. Because full conversion of 3c with CS2 requires long reaction times, an alternative synthetic route is reported herein, involving the conversion of 2 with phosphane dithiocarboxylates TerR(1)-C(S)SK (5), enabling synthetic access to a wider range of phosphane arsanyldithiocarboxylates. These interpnictogen dithiocarboxylates show an interesting bonding situation with a significantly elongated As-S bond due to negative hyperconjugation within the molecule. All products along the reaction path were fully characterized.

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