Phosphonium-Substituted Diphosphaindenylide (PPI): Exploration of Biradical Character and Ligand Properties.

Invited for the cover of this issue is the group of Peter Coburger at the Technical University of Munich. The image, painted by Dr. Christoph Selg, depicts the bonding relationships in a biradicaloid chromium complex as a staircase, with the people symbolizing the two-way flow of electrons between the ligand and the metal. Read the full text of the article at 10.1002/chem.202302970.

Phosphonium-substituted Diphosphaindenylide (PPI): Exploration of Biradical Character and Ligand Properties.

Starting from C6 H4 (PCl2 )2 and the TMS-substituted ylide (TMS)2 C=PR3 (TMS=trimethylsilyl, R=p-tolyl), the phosphonium-substituted diphosphaindenylide PPI was prepared in two steps. CASSCF calculations as well as the reactivity toward diphenyl acetylene suggest a notable biradical character in PPI. Reaction with [Cr(CO)3 (MeCN)3 ] affords the complex [Cr(CO)3 (η5 -PPI)] (5). This complex was employed to explore the ligand properties of PPI, which demonstrates considerable potential through the combination of strong metal-ligand interactions and the possibility of a pronounced indenyl effect.

Bis(imidazolium)-1,3-diphosphete-diide: A Building Block for FeC2 P2 Complexes and Clusters.

Reaction of the 6π-electron aromatic four-membered heterocycle (IPr)2 C2 P2 (1) (IPr=1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) with [Fe2 CO9 ] gives the neutral iron tricarbonyl complex [Fe(CO)3 -η3 -{(IPr)2 C2 P2 }] (2). Oxidation with two equivalents of the ferrocenium salt, [Fe(Cp)2 ](BArF24 ), affords the dicationic tricarbonyl complex [Fe(CO)3 -η4 -{(IPr)2 C2 P2 }](BArF24 )2 (4). The one-electron oxidation proceeds under concomitant loss of one CO ligand to give the paramagnetic dicarbonyl radical cation complex [Fe(CO)2 -η4 -{(IPr)2 C2 P2 }](BArF24 ) (5). Reduction of 5 allows the preparation of the neutral dicarbonyl complex [Fe(CO)2 -η4 -{(IPr)2 C2 P2 }] (6). An analysis by various spectroscopic techniques (57 Fe Mössbauer, EPR) combined with DFT calculations gives insight into differences of the electronic structure within the members of this unique series of iron carbonyl complexes, which can be either described as electron precise or Wade-Mingos clusters.

N-Heterocyclic Carbene Stabilized Dicarbondiphosphides: Strong Neutral Four-Membered Heterocyclic 6π-Electron Donors.

In contrast to cyclic π-conjugated hydrocarbons, the coordination chemistry of inorganic heterocycles is less developed. Dicarbondiphosphides stabilized by N-heterocyclic carbenes (NHCs) NHC→C2 P2 ←NHC (1 a,b) (NHC=IPr or SIPr) contain a four-membered C2 P2 ring with an aromatic 6π-electron configuration. These heterocycles coordinate to a variety of complex fragments with metals from groups 6, 9, and 10, namely [M0 (CO)3 ] (M=Cr, Mo), [CoI (CO)2 ]+ , or [NiII Br2 ], through an η4 -coordination mode, leading to complexes 2 a,b, 3 a,b, 5 a,b, and 6 a,b, respectively. These complexes were characterized by X-ray diffraction methods using single crystals, IR spectroscopy, and DFT calculations. In combination these methods indicate that 1 a,b behave as exceptionally strong 6π-electron donors.

Correction: Increasing steric demand through flexible bulk - primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones.

Correction for 'Increasing steric demand through flexible bulk - primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones' by Jonas Bresien et al., Dalton Trans., 2019, 48, 3786-3794.

Increasing steric demand through flexible bulk - primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones.

Sterically demanding primary phosphanes of the type RBhp-PH2 (Bhp = 2,6-bis(benzhydryl)-4-R-phenyl; R = Me, tBu) could be prepared in high yields by modification of synthetic protocols of established bulky phosphanes. The Bhp substituents simultaneously exhibit extensive steric expansiveness and high degrees of flexibility compared to other 2,6-substituted phenyl backbones, enabling a range of different-sized atoms and functionalities to be located between the flanking benzhydryl moieties. Therefore, it was also possible to isolate and fully characterize several halogenated precursors, a diazonium intermediate, as well as a dihalostibane.