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This research explores the cycloaddition reactions of titanocene-phosphinidene complexes with alkynes to produce phosphatitanacycles.

April 16, 2026Open Access

On Phosphatitanacycles

Key Points

This research explores the cycloaddition reactions of titanocene-phosphinidene complexes with alkynes to produce phosphatitanacycles.
Utilized titanocene-phosphinidene and diphosphanediide complexes.
Conducted [2 + 2] and [3 + 2] cycloaddition reactions with terminal alkynes.
Assessed reactivity with both aryl-substituted and aliphatic alkynes.
Investigated resulting metallacycles using spectroscopic and crystallographic methods.
Cp 2 Ti(PMe 3 )P Mes Ter yielded stable phosphatitanacyclobutene with various terminal alkynes.
Cp 2 Ti(P 2 Ar 2 ) primarily reacted with aryl-substituted alkynes possessing strong electron-withdrawing groups.
Characterization of the cyclic products provided insights into their stability and structure.

Abstract

Titanocene‐phosphinidene and diphosphanediide (or diphosphene) complexes Cp 2 Ti(PMe 3 )P Mes Ter and Cp 2 Ti(P 2 Ar 2 ) (Ar=Tipp, Dipp) undergo formal 2 + 2 or 3 + 2 cycloaddition reactions with terminal alkynes, respectively, to give the corresponding 4‐ and 5‐membered phosphatitanacycles. Cp 2 Ti(PMe 3 )P Mes Ter is shown to react selectively with aryl‐substituted and aliphatic terminal alkynes to give stable phosphatitanacyclobutene species, while the reactivity of Cp 2 Ti(P 2 Ar 2 ) is restricted to aryl‐substituted terminal alkynes featuring strong electron‐withdrawing substituents in para ‐position. These metallacycles were investigated spectroscopically and crystallographically.

On Phosphatitanacycles

Key Points

Abstract

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