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Steric Control in Reactions of N‐Heterocyclic Phosphorus Electrophiles with Pentacarbonyl Manganate(–I)
Author(s) -
Papendick Marius,
Feil Christoph M.,
Nieger Martin,
Gudat Dietrich
Publication year - 2018
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201800178
Subject(s) - steric effects , chemistry , electrophile , decarbonylation , ionic bonding , medicinal chemistry , covalent bond , metathesis , stereochemistry , organic chemistry , ion , catalysis , polymer , polymerization
Metathesis of Na[Mn(CO) 5 ] with N‐ t Bu and N‐Mes substituted, electrophilic N‐heterocyclic phosphane derivatives afforded in the first case an ionic N‐heterocyclic phosphenium (NHP) metalate and in the second case a covalent phosphenium complex. The products were characterized by analytical and spectroscopic data and the NHP complex as well by a single‐crystal X‐ray diffraction study. A DFT study allows relating the different outcome of the reactions studied with the energetics of the decarbonylation of the appropriate NHP metalates. Closer evaluation reveals steric factors as the key to explaining the observed behavior, and indicates that their impact displays close parallels to NHC chemistry.