Cyaphide

Structure of the first transition metal cyaphide complex

Cyaphide, P≡C−, is the phosphorus analogue of cyanide. It is not known as a discrete salt, however, In silico measurements reveal that the -1 charge in this ion is location mainly on carbon (0.65), as opposed to phosphorus.

Preparation

Organometallic complexes of cyaphide were first reported in 1992.[1] More recent preparations use two other routes:

From SiR3-functionalised phosphaalkynes

Treatment of the ɳ1-coordinated phosphaalkyne complex trans-[RuH(P≡CSiPh3)(dppe)2]+ with an alkoxide resulted in desilylation, followed by subsequent rearrangement to the corresponding carbon-bound cyaphide complex. [2] Cyaphide-alkynyl complexes are prepared similarly.[3]

From 2-phosphaethynolate anion (-OC≡P)

An actinide cyaphide complex can be prepared by C-O bond cleavage of the phosphaethynolate anion, the phosphorus analogue of cyanate.[4] Reaction of the uranium complex [((Ad,MeArO)3N)UIII(DME)] with [Na(OCP)(dioxane)2.5] in the presence of 2.2.2-cryptand results in the formation of a dinuclear, oxo-bridged uranium complex featuring a C≡P ligand.

See also

References

  1. ↑ Robert J. Angelici (2007). "Cyaphide (C≡P−): The Phosphorus Analogue of Cyanide (C≡N−)". Angew. Chem. Int. Ed. 46: 330–332. doi:10.1002/anie.200603724.
  2. ↑ Cordaro et al. (2006). "Making the True "CP" Ligand". Angew. Chem. Int. Ed. 45: 6159–6162. doi:10.1002/anie.200602499.
  3. ↑ "Synthesis and electronic structure of the first cyaphide-alkynyl complexes." Trathen et al. Dalton Trans. 2014, 43, 9004 - 9007 doi:10.1039/C4DT01108B
  4. ↑ Christopher J. Hoerger, Frank W. Heinemann, Elisa Louyriac, Laurent Maron, Hansjörg Grützmacher, Karsten Meyer (2017). "Formation of a Uranium-Bound η1-Cyaphide Ligand via Activation and C-O Bond Cleavage of Phosphaethynolate". Organometallics. 36: 4351–4354. doi:10.1021/acs.organomet.7b00590.
This article is issued from Wikipedia. The text is licensed under Creative Commons - Attribution - Sharealike. Additional terms may apply for the media files.