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.
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≡CSiPH3)(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,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
- PMID 17154215.
- PMID 16937421.
- PMID 24867599.
- doi:10.1021/acs.organomet.7b00590.)
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