96332-59-1

Upstream product

• 78129-68-7 2,2-dimethylpropylidynephosphine 
• 622-37-7 Phenyl azide 
• 108-86-1 bromobenzene 

Relevant academic research and scientific papers

One Co-ordinate Phosphorus Compounds: 1,3-Dipolar Cycloadditions with 2,2-Dimethylpropylidynylphosphine

1,3-Dipolar cycloadditions of azides, p-chlorobenzonitrile oxide, and methyl diazoacetate with 2,2-dimethylpropylidynylphosphine occur regiospecifically yielding cyclic 'aromatic' monoadducts: triaza-, oxaza-, and diaza-phospholes and the oxazaphosphole can react further with p-chlorobenzonitrile oxide to give a symmetrical phosphorus heterocycle.

Pyridyl-Functionalised 3H-1,2,3,4-Triazaphospholes: Synthesis, Coordination Chemistry and Photophysical Properties of Low-Coordinate Phosphorus Compounds

Novel conjugated, pyridyl-functionalised triazaphospholes with either tBu or SiMe3 substituents at the 5-position of the N3PC heterocycle have been prepared by a [3+2] cycloaddition reaction and compared with structurally related, triazole-based systems. Photoexcitation of the 2-pyridyl-substituted triazaphosphole gives rise to a significant fluorescence emission with a quantum yield of up to 12 %. In contrast, the all-nitrogen triazole analogue shows no emission at all. DFT calculations indicate that the 2-pyridyl substituted systems have a more rigid and planar structure than their 3- and 4-pyridyl isomers. Time-dependent (TD) DFT calculations show that only the 2-pyridyl-substituted triazaphosphole exhibits similar planar geometry, with matching conformational arrangements in the lowest energy excited state and the ground state; this helps to explain the enhanced emission intensity. The chelating P,N-hybrid ligand forms a ReI complex of the type [(N^N)Re(CO)3Br] through the coordination of nitrogen atom N2 to the metal centre rather than through the phosphorus donor. Both structural and spectroscopic data indicate substantial π-accepting character of the triazaphosphole, which is again in contrast to that of the all-nitrogen-containing triazoles. The synthesis and photophysical properties of a new class of phosphorus-containing extended π systems are described. Mix and match: Hitherto unknown pyridyl-functionalized triazaphospholes have been synthesized by a [3+2] cycloaddition reaction starting from phosphaalkynes and pyridyl-substituted azides (see figure). Both experiments and theoretical calculations established these compounds as novel π-conjugated organophosphorus derivatives for future optoelectronic applications.

PHOSPHORUS COMPOUNDS WITH UNUSUAL COORDINATION - 20. 1,2,3,4-TRIAZAPHOSPHOLES BY -CYCLOADDITION OF AZIDES TO A STABLE PHOSPHAALKYNE

The azides 2a-i undergo regiospecific -cycloaddition with the phosphaalkyne 1 to form the 1,2,3,4-triazaphospholes 3a-i; in the case of the reaction with 2j, an additional silyl shift occurs resulting in the formation of 4j.The latter product can be hydrolyzed to 6 which has also been prepared independently from 1 and hydrazoic acid (7).Flash vacuum pyrolyses of the 1,2,3,4-triazaphospholes 3c and 3e produce mixtures of the isomers 13a,b and 14a,b, respectively, from which the 1,2-azaphospholes 14 can be isolated as the major reaction products.