Dianionic Mononuclear Cyclo ‐P 4 Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo ‐P 4 Dianion in the Absence of Intramolecular Charge Transfer

Relative to other cyclic poly‐phosphorus species (that is, cyclo ‐P n ), the planar cyclo ‐P 4 group is unique in its requirement of two additional electrons to achieve aromaticity. These electrons are supplied from one or more metal centers. However, the degree of charge transfer is dependent on the nature of the metal fragment. Unique examples of dianionic mononuclear η 4 ‐P 4 complexes are presented that can be viewed as the simple coordination of the [ cyclo ‐P 4 ] 2− dianion to a neutral metal fragment. Treatment of the neutral, molybdenum cyclo ‐P 4 complexes Mo(η 4 ‐P 4 )I 2 (CO)(CNAr Dipp2 ) 2 and Mo(η 4 ‐P 4 )(CO) 2 (CNAr Dipp2 ) 2 with KC 8 produces the dianionic, three‐legged piano stool complexes, [Mo(η 4 ‐P 4 )(CO)(CNAr Dipp2 ) 2 ] 2− and [Mo(η 4 ‐P 4 )(CO) 2 (CNAr Dipp2 )] 2− , respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic η 6 ‐benzene complex (η 6 ‐C 6 H 6 )Mo(CO) 3 regarding the metal‐center valence state and electronic population of the planar‐cyclic ligand π system.