Stabilized borylenes (L2 BH:) with weakly π-accepting substituents L, such as phosphines, were previously believed to be unstable. In the current manuscript, we describe a series of complexes formally containing phosphine-stabilized borylene or boryl anion. contrast common trivalent boron compounds, boron-based ligands in this study act electron-donating ligands. The reported iron hydride exhibit unique reactivity pattern, undergoing reversible B-H reductive elimination concomitant oxidation...

The coordination chemistry of lanthanoids with neutral tertiary phosphine ligands is still largely underdeveloped, only few examples and none for some the lanthanoids, such as gadolinium. Therefore, formation organometallic lanthanum gadolinium complexes was investigated. Solvent-free precursors [Ln(COT)I] [LnCp3] (Ln = La, Gd) were reacted bisphosphines 1,2-bis(dimethylphosphino)ethane (dmpe) 1,2- bis(dimethylphosphino)methane (dmpm). resulting [Gd(COT)I(dmpe)], [{Gd(COT)(μ-I)}2(μ-dmpm)],...

Unusual binding properties, enabling the stabilization of elusive species, and beneficial properties for homogeneous catalysts have been predicted demonstrated ligand-stabilized main group fragments, such as carbodiphosphoranes -carbenes. However, quantification comparison their by experimental means still represent major challenges. In this article, we describe a series iridium(III) pincer complexes type [(PEP)IrCl(CO)(H)]q donor strength central E (q = 0, +1, +2). Our investigations show...

The (R₃P)₂HB-moiety in a palladium(<sc>ii</sc>) pincer complex is demonstrated to be L-type ligand and compared with other bonding types.

Abstract Based on the synthesis and characterization of a series new (poly‐)selenide salts, classification anionic (poly‐)selenide‐containing compounds is proposed. The were categorized according to these classes. Synthetic approaches organic cation‐stabilized that have been already known from literature are reviewed, along with crystal structures some spectroscopic data, an experimental theoretical approach towards dichroism observed in triselenides.

Abstract A series of iron(II) dihalogenide complexes with two different bisphosphinoethane ligands is reported. In the case 1,2‐bis(diphenylphosphanyl)ethane (dppe), depending on stoichiometry, tetrahedral [(μ‐dppe)FeCl 2 ] n and octahedral trans ‐[(dppe) FeCl are formed. The polymeric complex , iron in a environment, preferentially reacts chelating amines to give diphosphine complex, ], amine complexes. With sterically more demanding 1,2‐bis(diisopropylphosphanyl)ethane (dippe), monomeric...

Abstract Quantum theoretical studies show that the extremely high proton affinity at metal center of unusual T‐shaped (LXL)Au I –pincer complex, consisting a carbazole framework and two mesoionic carbenes, is caused by relativistic effects. This brings basicity Au in line with electron‐rich nitrogen atom ring system, resulting one highest affinities for neutral molecule.

Abstract Stabilisierte Borylene (L 2 BH:) mit schwach π‐akzeptierenden Substituenten L, wie Phosphanen, galten bisher als instabil. Hier beschreiben wir eine Serie von Komplexen, die formal ein Phosphan‐stabilisiertes Borylen oder Boryl‐Anion Liganden enthalten. Im Unterschied zu gängigen dreibindigen Bor‐Verbindungen agieren hier beschriebenen elektronendonierende Liganden. Die erhaltenen Eisen‐Hydrid‐Komplexe weisen ungewöhnliche Reaktivität auf und reagieren reversibel unter reduktiver...

Abstract Reduction of chalcogen‐rich Pb:Ch (1:2) phases in ethane‐1,2‐diamine ( en ) by elemental alkali metals results the formation solutions [Pb 2 Ch 3 ] 2– high purity and abundance. In contrast, application same reaction conditions to a binary Bi:Te phase yields mononuclear [BiTe 3– anion. Instead expected [Tl Te 4– or anions, analogous reactions with Tl:Te (1:1) end up C–C‐bond cleavage solvent salt telluridocyanate (N≡C–Te) – Side cesium are presented metalate investigated NMR spectroscopy.

Abstract Easy‐to‐prepare η 2 ‐coordinated phosphine‐borane ligands are demonstrated to liberate hydrogen upon treatment with different σ‐donor/π‐acceptor (CO, t BuNC, CN − ). Depending on the utilized ancillary ligand, reaction pathways observed, ranging from simple hydride protonation iron–boron bond formation and subsequent rearrangement pincer‐type based a tricoordinate boron centre. The last‐named reactivity is in line formal umpolung at centre Lewis acidic borane basic boron‐based donor ligand.

A series of Ni complexes [Ni(Cl)2(PR3)2] with R = Me (1-Me), nPr (1-nPr), and nBu (1-nBu) nickelocenes [Ni(η5-C5H4R′)2] R′ H (2-H), (2-Me), SiMe3 (2-SiMe3) were synthesized characterized. From these complexes, the synthesis [NiCl(PR3)(η5-C5H4R′)] Me, (3-Me), R= nBu, (3-nBu), nPr, (3-nPr), Et, (4), (5) was achieved. All fully characterized, including single crystal X-ray crystallography. Complexes 3-R, 4, 5 then used to obtain homobimetallic rare examples unbridged Ni–Ni bonds...

We report the synthesis and characterization of uranium(IV) thorium(IV) mesoionic carbene complexes [An{N(SiMe3)2}2(CH2SiMe2NSiMe3){MIC}] (An = U, 4U Th, 4Th; MIC {CN(Me)C(Me)N(Me)CH}), which represent rare examples actinide linkages first example a thorium complex. Complexes 4Th were prepared via C–H activation intramolecular cyclometallation reaction halides, with concomitant formal 1,4-proton migration an N-heterocyclic olefin (NHO). Quantum chemical calculations suggest that An–carbene...

An iron pincer complex containing a hemi-labile (R3 P)2 BH2 group exhibits temperature-switchable reactivity patterns: reversible B-H activation concomitant with P-B bond cleavage is observed at room temperature. Below 4 °C, intra- and intermolecular C-H pathways are becoming faster more dominant. Mechanistic investigations reveal that the lability of in combination exothermic formation σ-bonded complexes responsible for switchable activation. Finally, protocol an iron-catalyzed H/D-exchange...

A systematic quantum chemical study of the bonding in d6 -transition-metal complexes, containing phosphine-stabilized, main-group-element fragments, (R3 P)2 E, as ligands (E=AlH, BH, CH+ , C), is reported. By using energy decomposition analysis, it demonstrated that a strong M-E bond accompanied by weak P-E bonds, and vice versa. Although Al-M is, for example, found to be very strong, Al-P suggests corresponding metal complexes will not stable towards phosphine dissociation. The interaction...

Abstract Two missing compounds within the binary K-Se system have been synthesized and structurally characterized by means of single-crystal diffraction. β -K 2 Se comprises cell parameters that are in line with predictions made from series α / -A Ch x . K 4 , contrast, incorporates “Se 5 2– ” chains 50% occupation terminal selenium atoms, has on a rather unconventional solvothermal pathway employing successively mercury ethylene dithiol as solvents.

We report the synthesis and characterisation of a series rare-earth mesoionic carbene complexes, [RE{N(SiMe3 )2 }3 {CN(Me)C(Me)N(Me)CH}] (3RE, RE=Sc, Ce, Pr, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), greatly expanding limited library f-block complexes. These complexes were prepared by treatment parent RE-triamides with an N-heterocyclic olefin (NHO), where NHO backbone proton undergoes formal 1,4-proton migration to NHO-methylene group. For all RE(III) metals, as expected, quantum chemical...

Abstract A series of ten uranium(III) complexes with cyclopentadienyl and monodentate phosphine ligands [UCp 3 (PR )] R=Me, Et, n Pr, i t Bu, Ph, Cy, F CF was investigated using density functional theory calculations. The ligand dissociation energies were calculated, as well bonding analysis the uranium‐phosphorus bond performed, molecular orbitals, orders, quantum atom in molecules (QTAIM) energy decomposition natural orbitals for chemical valence (EDA‐NOCV). It found that orders correlate...

Abstract Phases of nominal composition PbCh·Ch (Ch: chalcogen), Bi 2 Te 3 ·Te, and Tl Te·Te are prepared by fusion the elements in quartz ampoules under Ar prior to their reduction K a solution en 18‐crown‐6.