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.
The word "cyaphide" was first coined in 1992, by analogy with cyanide.[1]
Preparation
[edit]Organometallic complexes of cyaphide were first reported in 1992.[2] More recent preparations use two other routes:
From SiR3-functionalised phosphaalkynes
[edit]Treatment of the η1-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.[3] Cyaphide-alkynyl complexes are prepared similarly.[4]
From 2-phosphaethynolate anion (−OC≡P)
[edit]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 [((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
[edit]References
[edit]- ^ 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.
- ^ 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; et al. (2006). "Making the True "CP" Ligand". Angewandte Chemie International Edition. 45 (37): 6159–6162. doi:10.1002/anie.200602499. PMID 16937421.
- ^ 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. PMID 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. doi:10.1021/acs.organomet.7b00590.
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