Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 43, Pages 15329-15333Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201908885
Keywords
aromaticity; cyclo-P-4; isocyanide; molybdenum; phosphorus
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Funding
- U.S. National Science Foundation [CHE-1802646]
- Alexander von Humboldt Foundation
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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 eta(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(eta(4)-P-4)I-2(CO)(CNArDipp2)(2) and Mo(eta(4)-P-4)(CO)(2)(CNArDipp2)(2) with KC8 produces the dianionic, three-legged piano stool complexes, [Mo(eta(4)-P-4)(CO)(CNArDipp2)(2)](2-) and [Mo(eta(4)-P-4)(CO)(2)(CNArDipp2)](2-), respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic eta(6)-benzene complex (eta(6)-C6H6)Mo(CO)(3) regarding the metal-center valence state and electronic population of the planar-cyclic ligand pi system.
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