Tert-butylphosphaacetylene
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| Identifiers | |||
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78129-68-7 
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| 3D model (Jmol) | Interactive image | ||
| ChemSpider |
127788 
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| PubChem | 144845 | ||
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| Properties | |||
| C5H9P | |||
| Molar mass | 100.10 g·mol−1 | ||
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Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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 (what is ?) |
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tert-Butylphosphaacetylene is an organophosphorus compound. Abbreviated t-BuCP, it was the first example of an isolable phosphaalkyne. Prior to its synthesis, the double bond rule had suggested that elements of Period 3 and higher were unable to form double or triple bonds with lighter main group elements because of weak orbital overlap. The successful synthesis of t-BuCP discredited much of the double bond rule and opened new studies into the formation of unsaturated phosphorus compounds.
The synthesis of t-BuCP entails the reaction of pivaloyl chloride and P(SiMe3)3. The reaction proceeds via the intermediacy of a bis(trimethylsilyl)pivaloylphosphine, which undergoes a 1,3-silyl shift to form E- or Z-phosphoalkene isomers. Carrying out the phosphoalkene reaction at 120-200 °C in the presence of catalytic amounts of solid NaOH forms the final t-BuCP product.
Phosphaalkynes possessing a C≡P bonded to bulky aryl groups are also known, e.g. Mes*C≡P and P≡C(Tript)C≡P are known to possess C≡P bond lengths of 1.516 and 1.532 Å, respectively (see below). While t-BuCP possesses a carbon-phosphorus bond length of 1.536 Å and a first ionization potential (π MO) of 9.70eV, H-C≡P possesses a C≡P bond length of 1.5421Å and a first ionization potential (π MO) of 10.79eV.
These physical properties produce characteristic reactivity differences between the two species: tert-butylphosphaacetylene is a stable volatile liquid (b.p. 61 °C), and phosphaacetylene readily reacts to form elemental phosphorus. It has been proposed that isophosphaalkynes (R-P≡C) are produced as intermediates during the syntheses of phosphaalkynes. Such isomeric species have never been isolated.
With their characteristic C-P triple bonds, the phosphorus atoms of phosphaalkynes such as tert-butylphosphaacetylene exhibit reactivities similar to nitriles, despite the significant differences between the radii of P (1.09 Å) and N (0.71 Å). At temperatures above 130 °C, the phosphaalkyne undergoes cyclotetramerization. To some extent its reactivity more closely resembles the reactions of alkynes.
tert-Butylphosphaacetylene can bind to metals via various coordination modes to give inorganic and organometallic complexes. These complexes utilize either the triple bond or the nonbonding electrons on P.
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