Cyaphide Explained
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.
The word "cyaphide" was first coined in 1992, by analogy with cyanide.[1]
Preparation
Organometallic complexes of cyaphide were first reported in 1992.[2] More recent preparations use two other routes:
From SiR3-functionalised phosphaalkynes
Treatment of the η1-coordinated phosphaalkyne complex trans - with an alkoxide resulted in desilylation, followed by subsequent rearrangement to the corresponding carbon-bound cyaphide complex.[3] Cyaphide-alkynyl complexes are prepared similarly.[4]
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.[5] Reaction of the uranium complex [{{chem2|((^{Ad,Me}ArO)3N)U^{III}(DME)}}] with [{{chem|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
Notes and References
- Jun . Hyoung . Young . Victor G. . Angelici . Robert J. . A phosphorus analog (C≡P−) of a bridging cyanide (C≡N−) ligand: synthesis and structure of (Cl)(PEt3)2Pt(μ-C≡P)Pt(PEt3)2 . Journal of the American Chemical Society . 114 . 25 . 1992 . 0002-7863 . 10.1021/ja00051a050 . 10064–10065.
- Robert Angelici. Robert J. Angelici. 2007. Cyaphide (C≡P−): The Phosphorus Analogue of Cyanide (C≡N−). Angew. Chem. Int. Ed.. 46. 3. 330–332. 10.1002/anie.200603724. 17154215. free.
- Cordaro. etal. 2006. Making the True "CP" Ligand. Angewandte Chemie International Edition. 45. 37. 6159–6162. 10.1002/anie.200602499. 16937421. free.
- Synthesis and electronic structure of the first cyaphide-alkynyl complexes . Trathen . etal . Dalton Transactions . 2014 . 43 . 24 . 9004–9007 . 10.1039/C4DT01108B. 24867599 .
- 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. 10.1021/acs.organomet.7b00590.
