Side-on coordination of diphosphorus to a mononuclear iron center

The diagonal relationship in the periodic table between phosphorus and carbon has set an expectation that the triple-bonded diatomic diphosphorus molecule (P ) should more closely mimic the attributes of acetylene (HC≡CH) rather than its group 15 congener dinitrogen (N ). Although acetylene has well...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2022-03, Vol.375 (6587), p.1393-1397
Main Authors: Wang, Shuai, Sears, Jeffrey D, Moore, Curtis E, Rheingold, Arnold L, Neidig, Michael L, Figueroa, Joshua S
Format: Article
Language:English
Subjects:
Alkynes
Bonding
Coordination
Crystallography
Iron
Periodic table
Phosphorus
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Summary:The diagonal relationship in the periodic table between phosphorus and carbon has set an expectation that the triple-bonded diatomic diphosphorus molecule (P ) should more closely mimic the attributes of acetylene (HC≡CH) rather than its group 15 congener dinitrogen (N ). Although acetylene has well-documented coordination chemistry with mononuclear transition metals, coordination complexes that feature P bound to a single metal center have remained elusive. We report the isolation and x-ray crystallographic characterization of a mononuclear iron complex featuring P coordination in a side-on, η -binding mode. An analogous η -bound bis-timethylsilylacetylene iron complex is reported for comparison. Nuclear magnetic resonance, infrared, and Mössbauer spectroscopic analysis-in conjunction with density functional theory calculations-demonstrate that η -P and η -acetylene ligands exert a similar electronic demand on mononuclear iron centers but exhibit different reactivity profiles.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.abn7100