Ring Expansions of Nonpolar Polyphosphorus Rings

The reaction of the phosphinidene complex [Cp*P{W(CO)₅ }₂ ] (1 a) (Cp*=C₅ Me₅ ) with the anionic cyclo-P_n ligand complex [(η³ -P₃ )Nb(ODipp)₃ ]^- (2, Dipp=2,6-diisopropylphenyl) resulted in the formation of [{W(CO)₅ }₂ {μ₃ ,η^3:1:1 -P₄ Cp*}Nb(ODipp)₃ ]^- (3), which represents an unprecedented example of a ring expansion of a polyphosphorus-ligand complex initiated by a phosphinidene complex. Furthermore, the reaction of the pnictinidene complexes [Cp*E{W(CO)₅ }₂ ] (E=P: 1 a, As: 1 b) with the neutral complex [Cp'''Co(η⁴ -P₄ )] (Cp'''=1,2,4-tBu₃ C₅ H₂ ) led to a cyclo-P₄ E ring (E=P, As) through the insertion of the pentel atom into the cyclo-P₄ ligand. Starting from 1 a, the two isomers [Cp'''Co(μ₃ ,η^4:1:1 -P₅ Cp*){W(CO)₅ }₂ ] (5 a,b), and from 1 b, the three isomers [Cp'''Co(μ₃ ,η^4:1:1 -AsP₄ Cp*){W(CO)₅ }₂ ] (6 a-c) with unprecedented cyclo-P₄ E ligands (E=P, As) were isolated. The complexes 6 a-c represent unique examples of ring expansions which lead to new mixed five-membered cyclo-P₄ As ligands. The possible reaction pathways for the formation of 5 a,b and 6 a-c were investigated by a combination of temperature-dependent ³¹ P{¹ H} NMR studies and DFT calculations.