Chemistry:Cyaphide
2(CP)
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.
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
- phosphaalkyne (P≡CR)
- Methylidynephosphane
- Cyaarside
References
- ↑ 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.
- ↑ Cordaro (2006). "Making the True "CP" Ligand". Angewandte Chemie International Edition 45 (37): 6159–6162. doi:10.1002/anie.200602499. PMID 16937421.
- ↑ Trathen (2014). "Synthesis and electronic structure of the first cyaphide-alkynyl complexes". Dalton Transactions 43 (24): 9004–9007. doi:10.1039/C4DT01108B. PMID 24867599. http://sro.sussex.ac.uk/id/eprint/48848/1/DTc4dt01108b-acceptedMS.PDF.
- ↑ 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.
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