Chemistry:Cyaphide
Cyaphide, −
C≡P, is the phosphorus analogue of cyanide. The molecule features a triple bond between carbon and phosphorus. With weaker π bonds than cyanide, the cyaphide ion is more reactive than its lighter congener.[1] 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.[2]
Coordination Modes
The cyaphide anion has been found in various coordination modes. The terminal σ-complex involves a metal–carbon bond.[3] A side-on η2 interaction has also been observed, in which the metal fragment donates electron density into the ligands low-lying π* orbital.[3]
Preparation
Organometallic complexes of cyaphide were first reported in 1992.[4] More recent preparations use two other routes:
From SiR
3-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.[5] Cyaphide-alkynyl complexes are prepared similarly.[6]
From 2-phosphaethynolate anion (−
O–C≡P)
An actinide cyaphide complex can be prepared by C−O bond cleavage of the phosphaethynolate anion, the phosphorus analogue of cyanate.[7] 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 (R–C≡P)
- Methylidynephosphane (H–C≡P)
- Cyanide
- Cyaarside
References
- ↑ Wilson, Daniel W. N.; Urwin, Stephanie J.; Yang, Eric S.; Goicoechea, Jose M. (2021). "A Cyaphide Transfer Reagent". doi:10.1021/jacs.1c04417. https://pubs.acs.org/doi/10.1021/jacs.1c04417.
- ↑ Jun, Hyoung; Young, Victor G.; Angelici, Robert J. (1992). "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): 10064–10065. doi:10.1021/ja00051a050. ISSN 0002-7863.
- ↑ 3.0 3.1 Görlich, Tim; Coburger, Peter; Yang, Eric S.; Goicoechea, Jose M.; Grützmacher, Hansjörg; Müller, Christian (2023-08-07). "The Chemistry of the Cyaphide Ion" (in en). Angewandte Chemie International Edition 62 (32). doi:10.1002/anie.202217749. ISSN 1433-7851. https://onlinelibrary.wiley.com/doi/10.1002/anie.202217749.
- ↑ 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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