Cyaphide

Cyaphide anion
−C≡P
Names
IUPAC name
Cyaphide
Other names
Methanidylidynephosphane
Identifiers
3D model (JSmol)
  • InChI=1S/CP/c1-2/q-1
    Key: UVQWQOUGJCVJLT-UHFFFAOYSA-N
  • [C-]#P
Properties
CP−
Molar mass 42.985 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Structure of the first transition metal cyaphide complex, RuH(dppe)2(CP)

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 SiR3-functionalised phosphaalkynes

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.[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,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

References

  1. ^ Wilson, Daniel W. N.; Urwin, Stephanie J.; Yang, Eric S.; Goicoechea, Jose M. (2021). "A Cyaphide Transfer Reagent". Journal of the American Chemical Society. doi:10.1021/jacs.1c04417. PMC 8297854. PMID 34190545.
  2. ^ 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. ^ a b Görlich, Tim; Coburger, Peter; Yang, Eric S.; Goicoechea, Jose M.; Grützmacher, Hansjörg; Müller, Christian (2023-08-07). "The Chemistry of the Cyaphide Ion". Angewandte Chemie International Edition. 62 (32). doi:10.1002/anie.202217749. hdl:20.500.11850/616020. ISSN 1433-7851.
  4. ^ 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.
  5. ^ Cordaro; et al. (2006). "Making the True "CP" Ligand". Angewandte Chemie International Edition. 45 (37): 6159–6162. doi:10.1002/anie.200602499. PMID 16937421.
  6. ^ 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.
  7. ^ 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.{{cite journal}}: CS1 maint: multiple names: authors list (link)

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