Syntheses, Characterization, and Multifaceted Coordination Chemistry of Hydrazonido Titanium Complexes.

The reaction of hydrazones with bis(π-η5:σ-η1-pentafulvene)titanium complexes leads to both hydrazonido and hydrazido complexes depending on the interaction of the hydrazone with the fulvene ligand of the metal complex. The molecular structures mostly reveal κ2N,N side-on coordination of the hydrazonido ligand due to the deprotonation of the N-H bond by one of the fulvene moieties. Instead of deprotonation, the reaction of the bis(adamantylidene fulvene)titanium complexes with cinnamon aldehyde phenylhydrazone leads to κ1N coordination. By using donating groups in the backbone of the hydrazone ligands, there are exceptions to this coordination mode due to the insertion of the C═N double bond into the Ti-Cexo bond of the pentafulvene moiety. Using 2-pyridinecarboxaldehyde phenylhydrazone, a formal κ3N,N,N ligand system is formed by the coordination of the pyridine nitrogen atom to the metal center via consecutive N-H deprotonation and insertion. Finally, the use of salicylaldehyde phenylhydrazone ultimately produces a complex with the κ3N,N,O coordination mode by double deprotonation of the hydrazone N-H and O-H functions. Because of its slow conversion to the final product, the intermediate was isolated as an insertion product with consecutive O-H deprotonation, showing a κ2N,O coordination mode of the hydrazido ligand.

Germaaluminocenes-Masked Heterofulvenes.

Germaaluminocenes are formed by salt metathesis reactions of dipotassium germacyclopentadienediides with pentamethylcyclopentadienylaluminum dichloride. The reactivity pattern of these sandwich complexes is determined by the electrophilic central aluminum atom and by the nucleophilic dicoordinated germanium center. Surprisingly, the products formed by reactions with Lewis acids, Lewis bases, amphiphiles and compounds with polar double bonds are those expected from the reaction of a hypothetical aluminagermapentafulvene with these types of reagents. This suggests that germaaluminocenes are synthetic equivalents to these pentafulvenes.

Aluminagerma[5]pyramidanes-Formation and Skeletal Rearrangement.

The salt metathesis reaction of dipotassium germacyclopentadienediide with aluminum(III) dichlorides provides either half-sandwich alumole complexes of germanium(II) or aluminylene germole complexes. Their molecular structure and the delocalized bonding situation, revealed by density functional theory (DFT) calculations, are equally described as isomeric aluminagerma[5]pyramidanes with either the germanium or the aluminum atom in the apical position of the pentagonal pyramid. The product formation and the selectivity of the reaction depends on the third substituent of the aluminum dichloride. Aryl-substituents favor the formation of alumole complexes and Cp*-substituents that of the isomeric germole complexes. With amino-substituents at the aluminum atom mixtures of both isomers are formed and the positional exchange of the two heteroatoms is shown by NMR spectroscopy. The alumole complexes of germanium(II) undergo facile reductive elimination of germanium and form the corresponding alumoles.

Elemental Magnesium as an Early Transition Metal Substitute: From Pentafulvene Coordination to Deprotonation of Amines.

The reaction of magnesium turnings and 6,6-di-para-tolylpentafulvene was investigated. Under mild conditions, the magnesium dissolves, forming the MgII complex 1 with a π-η5 : σ-κ1 coordinating ligand of the dimerized pentafulvene, analyzed by NMR and XRD investigations. As a magnesium pentafulvene complex was a possible intermediate, amines were employed as intercepting agents. Thereby, the amines were formally deprotonated by elemental magnesium, yielding the first examples of Cp'Mg(THF)2 NR2 complexes. This reaction competes with the formation of 1 and a consecutive formal [1,5]-H-shift forming an ansa-magnesocene. Employing amines with low basicity gave quantitative conversion to the amide complexes.

Geometrically Deformed and Conformationally Rigid Phosphorus Trisamides Featuring an Unsymmetrical Backbone.

Nonclassical P(III) centers have attracted much attention in recent years. Incorporating a P(III) center in a rigid bicyclic platform offers a particularly attractive way to invoke significant geometric distortion of the phosphorus atom that may in turn induce unusual reactivity. Although still relatively scarcely explored, phosphorus centers enforced in a non-C3 symmetry have gained significant traction lately. However, the current scaffolds are based on a relatively limited set of design principles and ligand platforms associated therewith. This work is focussed on the synthesis as well as versatile oxidation, addition and coordination chemistry of a geometrically distorted P(III) species featuring a synthetically modular, nonsymmetric trisamine platform derived from 2-(methylamino)-N-(2-(methylamino)phenyl)benzenesulfonamide.

Vanadium Pentafulvene Complexes: Synthon for Unprecedented VanadoceneIII Derivatives.

The benzene ligand at CpV(η6 -C6 H6 ) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 a and 2 b) and benzofulvene complexes (3 a and 3 b). The molecular structures of the target compounds suggest a π-η5 :σ-η1 coordination mode with a vanadiumIII center. With the sterically low demanding 6,6-dimethylpentafulvene, a C-H activation at the leaving ligand is observed, yielding the ring-substituted vanadoceneII 4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadoceneIII compounds were synthesized: Under mild conditions, E-H splitting of 4-tert-butylphenol, diphenylamine, and 2,6-diisopropylaniline yield well characterized examples of rare vanadoceneIII phenolate and amide complexes. Insertion reactions into the V-Cexo bond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4-chlorobenzonitril and N,N'-dicyclohexylcarbodiimide.

Density Functional Theory Calculations for Multiple Conformers Explaining the Regio- and Stereoselectivity of Ti-Catalyzed Hydroaminoalkylation Reactions.

Hybrid Density Functional Theory (DFT) calculations for multiple conformers of the insertion reactions of a methylenecyclopropane into the Ti-C bond of two differently α-substituted titanaaziridines explain the experimentally observed differences in regioselectivity between catalytic hydroaminoalkylation reactions of methylenecyclopropanes with α-phenyl-substituted secondary amines and corresponding stoichiometric reactions of a methylenecyclopropane with titanaaziridines, which can only be achieved with α-unsubstituted titanaaziridines. In addition, the lack of reactivity of α-phenyl-substituted titanaaziridines as well as the diastereoselectivity of the catalytic and stoichiometric reactions can be understood.

Stereoselective Synthesis of Tertiary Allylic Amines by Titanium-Catalyzed Hydroaminoalkylation of Alkynes with Tertiary Amines.

Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn4 , Ph3 C[B(C6 F5 )4 ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary ß,γ-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.

Intramolecular Halo Stabilization of Silyl Cations-Silylated Halonium- and Bis-Halo-Substituted Siliconium Borates.

The stabilizing neighboring effect of halo substituents on silyl cations was tested for a series of peri-halo substituted acenaphthyl-based silyl cations 3. The chloro- (3 b), bromo- (3 c), and iodo- (3 d) stabilized cations were synthesized by the Corey protocol. Structural and NMR spectroscopic investigations for cations 3 b-d supported by the results of density functional calculations, which indicate their halonium ion nature. According to the fluorobenzonitrile (FBN) method, the silyl Lewis acidity decreases along the series of halonium ions 3, the fluoronium ion 3 a being a very strong and the iodonium ion 3 d a moderate Lewis acid. Halonium ions 3 b and 3 c react with starting silanes in a substituent redistribution reaction and form siliconium ions 4 b and 4 c. The structure of siliconium borate 4 c2 [B12 Br12 ] reveals the trigonal bipyramidal coordination environment of the silicon atom with the two bromo substituents in the apical positions.

Radicals and Anions of Siloles and Germoles.

Invited for the cover of this issue is the group of Thomas Müller at the University of Oldenburg. The image shows the calculated spin distribution of a persistent silacyclopentadienyl radical. Read the full text of the article at 10.1002/chem.202101415.

Radicals and Anions of Siloles and Germoles.

The synthesis of persistent sila- and germacyclopentadienyl (silolyl- and germolyl-) radicals by careful stoichiometric reduction of the corresponding halides with potassium is reported. The radicals were characterized by EPR spectroscopy and trapping reactions. The reduction of tris(trimethylsilyl)silyl-substituted halides was successful while smaller substituents (i. e., t-Butyl, Ph) gave the corresponding dimers. The EPR spectroscopic parameter of the synthesized tetrolyl radicals indicate only small spin delocalization to the butadiene unit due to cross-hyperconjugation. Silolyl- and germolyl anions are unavoidable byproducts and are isolated in the form of their potassium salts and characterized by X-ray crystallography. The comparison of the molecular structures of two closely related potassium silolides provided an example for different coordination of the potassium cation to the silolyl anion (η1 vs. η5 coordination) that triggers the switch between delocalized and localized states.

Intermolecular Hydroaminoalkylation of Alkynes.

Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl- and dialkylalkynes as well as a terminal alkyne take place with N-benzylanilines, N-alkylanilines, and N-alkylbenzylamines.

Titanium-Catalyzed Intermolecular Hydroaminoalkylation of Alkenes with Tertiary Amines.

The first cationic titanium catalyst system for the intermolecular hydroaminoalkylation of alkenes with various tertiary alkylamines is presented. Corresponding reactions which involve the addition of the α-C-H bond of a tertiary amine across the C-C double bond of an alkene take place at temperatures close to room temperature with excellent regioselectivity to deliver the branched products exclusively. Interestingly, for selected amines, α-C-H bond activation occurs not only at N-methyl but also at N-methylene groups.

Chiral Memory in Silyl-Pyridinium and Quinolinium Cations.

Pyridine- and quinoline-stabilized silyl cations have been prepared, and their structure in condensed phases unambiguously assigned using 1H, 13C, 15N, 29Si, and 1H DOSY NMR as well as X-ray diffraction studies. Solid state structures thus show in both cases a stabilization of the cationic silicon center through an N-Si interaction and formation of a highly strained four-membered ring system. Chiral memory at the silicon atom in these heterocycle-stabilized silyl cations was also established, leading to various levels of selectivity depending on the nature of the heterocycle. Lowest energy conformations of the starting silanes obtained through DFT calculations, along with the isolation and characterization of the Si-centered chiral silyl cation intermediates, finally allowed to propose a plausible hypothesis as to the configurational stability of these silyl cations.

Titanium-Catalyzed Hydroaminoalkylation of Ethylene.

The first examples of titanium-catalyzed hydroaminoalkylation reactions of ethylene with secondary amines are presented. The reactions can be achieved with various titanium catalysts and they do not require the use of high pressure equipment. In addition, the first solid-state structure of a titanapyrrolidine that is formed by insertion of an alkene into the Ti-C bond of a titanaaziridine is reported.

Chiral Chalcogenyl-Substituted Naphthyl- and Acenaphthyl-Silanes and Their Cations.

Cyclic silylated chalconium borates 13[B(C6 F5 )4 ] and 14[B(C6 F5 )4 ] with peri-acenaphthyl and peri-naphthyl skeletons were synthesized from unsymmetrically substituted silanes 3, 4, 6, 7, 9 and 10 using the standard Corey protocol (Chalcogen Ch=O, S, Se, Te). The configuration at the chalcogen atom is trigonal pyramidal for Ch=S, Se, Te, leading to the formation of cis- and trans-isomers in the case of phenylmethylsilyl cations. With the bulkier tert-butyl group at silicon, the configuration at the chalcogen atoms is predetermined to give almost exclusively the trans-configurated cyclic silylchalconium ions. The barriers for the inversion of the configuration at the sulfur atoms of sulfonium ions 13 c and 14 a are substantial (72-74 kJ mol-1 ) as shown by variable temperature NMR spectroscopy. The neighboring group effect of the thiophenyl substituent is sufficiently strong to preserve chiral information at the silicon atom at low temperatures.

Spin Transition of an Iron(II) Organoborate Complex in Different Polymorphs and in Vacuum-Deposited Thin Films: Influence of Cooperativity.

Two polymorphic modifications (1-I and 1-II) of the new spin crossover (SCO) complex [Fe{H2B(pz)(pypz)}2] (pz = pyrazole, pypz = pyridylpyrazole; 1) were prepared and investigated by differential scanning calorimetry (DSC), magnetic measurements, Mößbauer, vibrational, and absorption spectroscopy as well as single-crystal and X-ray powder diffraction. DSC measurements reveal that upon heating the thermodynamically metastable form 1-II to ∼178 °C it transforms into 1-I in an exothermic reaction, which proves that these modifications are related by monotropism. Both forms show thermal SCO with T1/2 values of 390 K (1-II) and 270 K (1-I). An analysis of the crystal structures of 1-II and the corresponding Zn(II) (2) and Co(II) (3) complexes that are isotypic with 1-I reveals that form II consists of dimers coupled by strong intramolecular π···π interactions, which is not the case for 1-I. In agreement with these findings, investigations of thin films of 1, where significant π···π interactions should be absent, reveal SCO behavior similar to that of 1-I. These results underscore the importance of cooperativity for the spin-transition behavior of this class of complexes.

Synthesis of Annulated Indolines by Reductive Fischer Indolization.

Cyclic ß-oxoesters and arylhydrazine derivatives were converted at ambient temperature under modified Fischer indolization conditions to furnish annulated indolines with quaternary bridgehead carbon center. Reaction conditions were Brønsted acidic (with CF3 CO2 H), but also reductive (with Et3 SiH). The latter reduced intermediate iminium ions under formation of the 2,3-dihydroindole product constitutions. Racemic products (13 examples) were obtained as single diastereoisomers with relative cis-configuration, which was proved in two cases by single-crystal X-ray structure analysis. Conversion of 4-bromo-1-indanone-2-carboxylate and 4-bromophenylhydrazine gave indeno[1,2-b]indolines with either 1-bromo, 8-bromo, or 1,8-dibromo substitution, which were further diversified by Suzuki coupling reactions with several arylboronic acids (nine examples).

Potassium Salts of 2,5-Bis(trimethylsilyl)-Germolide: Switching between Aromatic and Non-Aromatic States.

The reduction of a 1-mesityl-2,5-bis-trimethylsilylchlorogermole 8 with KC8 is reported. While the reaction with one equivalent of KC8 gave the dimer with a Ge-Ge bond 10, excess of KC8 (four equivalents) resulted in the formation of the potassium salt of the germole dianion, 11 with reductive cleavage of the Ge-C bond. Careful reduction with two equivalents of KC8 in THF provided the potassium salt of the planar germolide 5. Its solid-state structure revealed contact ion pairs with the potassium ion η5 -coordinated to the germacyclopentadienide ring. The molecular structure of the anion indicates a high degree of cyclic electron delocalization, in agreement with results from DFT calculations. Separation of the ion pair by complexation of the potassium ions with 18-crown-6 triggers the isomerization to germolide 6, which is characterized by a pyramidal coordination sphere of the germanium atom and a localized diene structure. The isomers 5 and 6 represent a rare example for a structurally manifested switch between a non-aromatic and an aromatic state induced by an external stimulus, in this case the complexation of the counter cation.

An Experimental Acidity Scale for Intramolecularly Stabilized Silyl Lewis Acids.

A new NMR-based Lewis acidity scale is suggested and its application is demonstrated for a family of silyl Lewis acids. The reaction of p-fluorobenzonitrile (FBN) with silyl cations that are internally stabilized by interaction with a remote chalcogenyl or halogen donor yields silylated nitrilium ions with the silicon atom in a trigonal bipyramidal coordination environment. The 19 F NMR chemical shifts and the 1 J(CF) coupling constants of these nitrilium ions vary in a predictable manner with the donor capability of the stabilizing group. The spectroscopic parameters are suitable probes for scaling the acidity of Lewis acids. These new probes allow for the discrimination between very similar Lewis acids, which is not possible with conventional NMR tests, such as the well-established Gutmann-Beckett method.