Cobalt(III)-containing penta-dentate "helmet"-type phthalogens: synthesis, solid-state structures and their thermal and electrochemical characterization.

Treatment of unsubstituted and substituted phthalonitrile (1a-d) with appropriate equivalents of sodium methoxide and ammonia afforded the corresponding 1,3-diiminoisoindolines (2a-d), which were converted to cobalt(III)-containing penta-dentate "helmet"-type phthalogens (3a-d) by the reaction with CoCl2·6H2O as templating agent in the inert solvent 1,2,4-trichlorobenzene. The identities of 2a-d and 3a-d were established by elemental analysis, infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and electrospray ionization mass spectrometry (ESI-MS). A computational study was performed to determine the most stable tautomeric form of 2a-c in the gas phase. The solid-state structures of 2b and 2c were determined by single crystal X-ray diffraction (SC-XRD) studies to confirm their existence in the stereoisomeric anti-form, which is aligned with quantum chemical computations. SC-XRD studies of 3a and 3b revealed a slightly distorted octahedral geometry around the CoIII ions which are coordinated by five N-donor atoms and one extra co-ligand, resulting in a coordination environment of CoN5Cl (3a) and CoN5O (3b), respectively. The thermal stabilities of 2a-d and 3a-d were investigated by thermogravimetric analysis (TGA) in the temperature range of 40-500 °C and 40-800 °C, respectively, revealing that 3a-d were converted to the parent cobalt(II)-containing phthalocyanines (4a-d), which was verified independently by furnace heating experiments. Moreover, the electrochemical behavior of 3a was studied exemplarily for the phthalogens by cyclic voltammetry and square wave voltammetry. This study showed that 4a (CoPc) is formed irreversibly by reducing 3a electrochemically.

Synthesis of Trialkylamines with Extreme Steric Hindrance and Their Decay by a Hofmann-like Elimination Reaction.

A number of amines with three bulky alkyl groups at the nitrogen, which surpass the steric crowding of triisopropylamine considerably, were prepared by using different synthetic methods. It turned out that treatment of N-chlorodialkylamines with organometallic compounds, for example, Grignard reagents, in the presence of a major excess of tetramethylenediamine offered the most effective access to the target compounds. The limits of this method were also tested. The trialkylamines underwent a dealkylation reaction, depending on the degree of steric stress, even at ambient temperature. Because olefins were formed in this transformation, it showed some similarity with the Hofmann elimination. However, the thermal decay of sterically overcrowded tertiary amines was not promoted by bases. Instead, this reaction was strongly accelerated by protic conditions and even by trace amounts of water. Reaction mechanisms, which were analyzed with the help of quantum chemical calculations, are suggested to explain the experimental results.

Nucleophilic Attack of Azide at Electrophilic Azides: Formation of N6 Units in Hexazene and Aminopentazole Derivatives.

With the help of selective 15 N labeling experiments, it has been confirmed that nucleophilic attack of azide at iminium-activated organic azides leads to short-lived hexazene intermediates. Such species do not only tend to a cleavage reaction with formation of N-azido compounds, but also undergo ring closure to generate unprecedented amidino-functionalized pentazoles. Thus, treatment of the parent Vilsmeier reagent with two equivalents of sodium azide creates an aminopentazole derivative as the main product, which is easily characterized by NMR spectroscopy.

Too Short-Lived or Not Existing Species: N-Azidoamines Reinvestigated.

Treatment of N-chlorodimethylamine with sodium azide in dichloromethane does not lead to N-azidodimethylamine, as thought for more than 50 years. Instead, surprisingly, (azidomethyl)dimethylamine is generated with good reproducibility. A plausible reaction mechanism to explain the formation of this product is presented. The reaction of lithium dibenzylhydrazide with tosyl azide does not result in the creation of an N-azidoamine, which can be detected by IR spectroscopy at ambient temperature, as it was claimed previously. Additional experiments with diazo group transfer to lithium hydrazides show that intermediate N-azidoamines are very short-lived or their formation is bypassed by direct generation of 1,1-diazenes via synchronous cleavage of two N-N bonds.

Steric Hindrance Underestimated: It is a Long, Long Way to Tri- tert-alkylamines.

Ten different processes (Methods A-J) were tested to prepare tertiary amines bearing bulky alkyl groups. In particular, SN1 alkylation of secondary amines with the help of 1-adamantyl triflate (Method D) and reaction of N-chlorodialkylamines with organometallic reagents (Method H), but also attack of the latter reagents at iminium salts, which were generated in situ by N-alkylation of imines (Method J), led to trialkylamines with unprecedented steric congestion. These products showed a restriction of the rotation about the C-N bond. Consequently, equilibration of rotamers was slow on the NMR time scale resulting in distinguishable sets of NMR data at room temperature. Furthermore, tertiary amines with bulky alkyl substituents underwent Hofmann-like elimination when heating in toluene to form an olefin and a secondary amine. Since the tendency to take part in this decay reaction correlated with the degree of steric hindrance around the nitrogen atom, Hofmann elimination at ambient temperature, which made the isolation of the tertiary amine difficult, was observed in special cases.

Rearrangement Reactions of Tritylcarbenes: Surprising Ring Expansion and Computational Investigation.

As a rule, acetylides and sulfonyl azides do not undergo electrophilic azide transfer because 1,2,3-triazoles are usually formed. We show now that treatment of tritylethyne with butyllithium followed by exposure to 2,4,6-triisopropylbenzenesulfonyl azide leads to products that are easily explained through the generation of short-lived tritylethynyl azide and its secondary product cyanotritylcarbene. Furthermore, it is demonstrated that tritylcarbenes generally do not produce triphenylethenes exclusively, as was stated in the literature. Instead, these carbenes always yielded also (diphenylmethylidene)cycloheptatrienes (heptafulvenes) as side products. This result is supported by static DFT, coupled cluster, and ab initio molecular dynamics calculations. From these investigations, the fused bicyclobutane intermediate was found to be essential for heptafulvene formation. Although the bicyclobutane is also capable of rearranging to the triphenylethene product, only the heptafulvene pathway is reasonable from the energetics. The ethene is formed straight from cyanotritylcarbene.