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Updated: Oct 7, 2025

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Published on: November 22, 2016
Synthesis of the open-shell 3d-transition metal(II) bis(phosphinidenide) [Mn{P(sIDipp)}2]
Ruth Weller1, Markus Balmer2, Carsten von Hänisch1
1Department of Chemistry, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, D-35032 Marburg, Germany. gunnar.werncke@chemie.uni-marburg.de.
Abstract:
The synthesis and characterization of the first homoleptic open-shell transition metal phosphinidenide is presented. By reacting [MnL2] (L = -N(SiMe3)2) with [(sIDipp)PK] (sIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), the formation of [Mn{P(sIDipp)}2] instead of the initially expected adduct [KMn{P(sIDipp)}L2] is observed. Interestingly, a solvent change from toluene to n-pentane leads to the formation of [(sIDipp)PK2(Et2O)4][MnL3] after work-up, which can be seen as intermediate in the formation process of [Mn{P(sIDipp)}2]. Contrary to manganese, the highly reducing phosphinidenide [(sIDipp)P]- cannot be stabilized in an analogous fashion by coordination to a low-coordinate high-spin iron(II) center.
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Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...