Synthesis and Reactivity of N‐Heterocyclic Carbene‐Phosphinidene Manganese Complexes
Year: 2025
Type: article
Abstract: The reaction of manganese pentacarbonyl bromide with the N‐heterocyclic carbene‐phosphinidene adduct (IDipp)PSiMe 3 afforded the tetracarbonyl complex [(IDipp)PMn(CO) 4 ] ( 1 ) with the release of Me 3 SiBr and CO (IDipp = 1,3‐bis(2,6‐diisopropylphenyl)‐imidazolin‐2‐ylidene). X‐ray crystallographic analysis revealed a trigonal‐bipyramidal coordination geometry with a short Mn─P bond, indicative of double bond character. CO substitution with phosphines, NHCs, and isocyanides yielded complexes [(IDipp)PMnL(CO) 3 ] ( 2 – 5 ) in which the ligands (L) occupy axial positions. Kinetic studies and DFT calculations support an associative substitution mechanism, analogous to the nitrosyl complex [Mn(NO)(CO) 4 ], demonstrating the ability of (NHC)P and NO ligands to modulate their electronic properties as either one‐ or three‐electron donors. Complex 1 also underwent phosphinidene transfer and chalcogenation reactions along the manganese‐phosphorus bond, resulting in metalladiphosphiranes ( 6 , 7 ) and metallaphospha‐chalcogeniranes ( 8 , 9 ) with three‐membered MnPP and MnPE (E = Se, Te) rings.
Source: Chemistry - A European Journal
Institution: Technische Universität Braunschweig
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,640
Funder: Deutsche Forschungsgemeinschaft
OpenAlex ID: W4408527147