期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 43, 页码 15329-15333出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201908885
关键词
aromaticity; cyclo-P-4; isocyanide; molybdenum; phosphorus
资金
- U.S. National Science Foundation [CHE-1802646]
- Alexander von Humboldt Foundation
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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