Cyaphide

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 located mainly on carbon (0.65), as opposed to phosphorus.

Structure of the first transition metal cyaphide complex, RuH(dppe)
2(CP)

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 η1-coordinated phosphaalkyne complex trans–[RuH(P≡CSiPH
3)(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,Me
ArO)
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 (3): 330–332. doi:10.1002/anie.200603724. PMID 17154215.
  2. Cordaro; et al. (2006). "Making the True "CP" Ligand". Angewandte Chemie International Edition. 45 (37): 6159–6162. doi:10.1002/anie.200602499. PMID 16937421.
  3. Trathen; et al. (2014). "Synthesis and electronic structure of the first cyaphide-alkynyl complexes" (PDF). Dalton Transactions. 43 (24): 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.CS1 maint: multiple names: authors list (link)
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