RESUMEN
A broad study on [4 + 1]- and [4 + 2]-cycloaddition reactions of a thiazole-2-thione-based 1,4-diphosphinine (1) is reported, with a special focus on reversible reactions. Reactions of 1 with group 13 carbenoids DippNacNacM (M = Al and Ga) afford [4 + 1] adducts that can be classified as Al and Ga phosphides or as 7-metalla-1,4-norbornadienes. Reactions of 1 with alkynes and alkenes result in [4 + 2]-cycloaddition, affording 1,4-diphosphabarrelenes. The effect of different dienophiles on the formation of 1,4-diphosphabarrelenes and their thermal [4 + 2]-cycloreversion reactions is studied from an experimental as well as theoretical point of view, opening the door for protection/deprotection strategies in this chemistry.
RESUMEN
7,8-Dihydro-1,4-diphosphabarrelene diselones and bis(NHCs) were synthesised and employed as multitopic P,Se and P,C ligands in coordination chemistry, benefitting from a unique bent, P-bridged topology, thus being promising new building blocks.
RESUMEN
1D and 2D NICS π . zz SOM ${{{\rm { NICS}}}_{{\rm { {\rm \pi}{}}}{\rm { .zz}}}^{{\rm { SOM}}}}$ (Sigma only model) calculations were performed on recently established tricyclic 1,4-diphosphinines as well as related benzene and pyrazine derivatives. The study was extended to evaluate the effect of the fused rings on the overall aromatic properties with a special focus on functional groups such as carbenes. The effect of non-aromatic heterocycles on the local ring current of the central ring is small, while aromatic heterocycles (e. g. NHC, imidazolium) lead to a global aromaticity. A higher sulfur content of the adjacent five-membered rings reduces the central ring current. The comparison to related tricyclic benzene and pyrazine derivatives showed that the 1,4-diphosphinine systems resemble more closely the situation in the benzene derivatives than the pyrazines. The effect of charged systems was studied using bis(TTF)-fused 1,4-diphosphinines and, according to NICS π . zz SOM ${{{\rm { NICS}}}_{{\rm { {\rm \pi}{}}}{\rm { .zz}}}^{{\rm { SOM}}}}$ values, the neutral form doesn't possess significant aromaticity but the tetracation resembles the global aromatic situation observed for other heterocycles in this study.
RESUMEN
The synthesis of five-membered P-heterocyclic iron(0) complexes possessing a P-H unit and two heteroatoms (E = O, N), directly bound to phosphorus, is described. Initial problems to achieve access via "classical" reduction of P-Cl bonds of P-heterocycle complexes, e.g., leading to P-P coupling, could be solved by a "combined two-step" reduction/complexation. The use of K[Fe(CO)4H] not only opened access to such heterocyclic phosphane Fe(CO)4 complexes but also allowed the synthesis of sterically non-shielded 'secondary' heterocyclic phosphane complexes. Spectroscopic and structural parameters are discussed.
RESUMEN
Reactions of tricyclic 1,4-diphosphinines 1,4 with LiOH, followed by protonation are reported. 1,3-Thiazole-2-thione-derived 1 enabled only observation of the first anionic addition product 2/3. On the other hand, imidazole-2-selone-annelated derivative 4 enabled the identification of the first (5) and second product (6) at low temperature. As water was eliminated upon warming in both cases, DFT calculations were performed to gain more insight into the reaction pathway(s).
RESUMEN
Dinuclear phosphinidene complexes bridging two transition metal centres are now well established. However, a phosphinidene bridging a metal centre and a main group Lewis acid has not yet been reported. Herein, we describe the generation of a highly reactive phosphinidene complex bridging a tungsten and a boron centre. Furthermore, the synthesis and dyotropic rearrangement of a P-borane adduct of an N-methylimidazole-stabilized neutral, electrophilic terminal phosphinidene complex is reported.
RESUMEN
Novel tricyclic 1,4-dihydro-1,4-phosphagermines (3a and 4a) were synthesised from Ge(NR2)2-bridged 1,3-imidazole-2-thione derivative 2a; all structures were crystallographically confirmed. In going from rather small alkyl substituents (Me, nBu) at the nitrogen centers of the 1,3-imidazole-2-thione units to sterically more demanding R = Mes and changing the employed Ge reagent from (R2N)2GeCl2 to R2NGeCl3 we achieved access to mixed functional bis(1,3-imidazole-2-thione)-substituted germanium derivative 2c. The latter was treated with MeLi and, subsequently, with PCl3 to yield a pentacyclic P,Ge-heterocycle (5); its formation was rationalized using DFT theoretical calculations.
RESUMEN
Phosphorus-bridged rigid, bent bis(N-heterocyclic) carbenes have not been reported, so far, despite having structural features that could make them interesting ligands in coordination and main group element chemistry. In previous reports, we had demonstrated that tuning of σ3- and σ4-phosphorus environments in planarised bis(NHCs) affects electronic properties and can provide additional coordination sites. Herein, we report on first examples of synthesis and conversion of 1,4-diphosphabarrelene-related compounds into rigid bent, doubly P-bridged bis(NHCs). The formation of main group element adducts with substrates from group 13, 14 and 15 illustrates opportunities to access novel scaffolds and to create nonplanar branching points. DFT calculations reveal the new bis(NHCs) to be good candidates as novel soft/hard ligands with up to four coordination sites. The synthesis of a dinuclear Fe(CO)4 complex is demonstrated. The thermal retro-[4 + 2] cycloaddition was theoretically and experimentally explored for a variety of ionic and zwitterionic 1,4-diphosphabarrelenes, and the generation and trapping of a dinuclear Fe(0) bis(NHC) complex with a tricyclic 1σ2,4 σ2-diphosphinine scaffold is presented.
RESUMEN
Herein, we describe the synthesis of a 1,2σ3λ3-oxaphosphetane from ethylene oxide and its reactions with alkyl halides to form ß-halo phosphane oxides in an Arbuzov-type reaction. When methyl triflate was used as a hard electrophile, cationic oligomerisation of 1,2-oxaphosphetanes was observed. DFT calculations indicate 1,2-oxaphosphetan-2-iums as intermediates and reveal differences between the Arbuzov and the potential Perkow reaction pathway.
RESUMEN
While the chemistry of phosphenium compounds, including metal complexes thereof, is very well established, few derivatives having a P-H bond have been described, yet. This work describes rational access to donor-stabilised phosphenium metal complexes possessing a P-H bond using protonation reactions of stable phosphinidene complex adducts. While most Brønsted-Lowry acids yield formal 1,1-addition products at the phosphorus centre under the loss of the donor, super-strong acids having weakly coordinating anions enable access to donor-stabilised P-H phosphenium complex salts. The latter possess N-methylimidazole as a donor (to phosphorus) and the N-P interaction has been studied theoretically.
RESUMEN
We describe nonmetal adducts of the phosphorus center of terminal phosphinidene complexes using classical C- and N-ligands from metal coordination chemistry. The nature of the L-P bond has been analyzed by various theoretical methods including a refined method on the variation of the Laplacian of electron density ∇2ρ along the L-P bond path. Studies on thermal stability reveal stark differences between N-ligands such as N-methyl imidazole and C-ligands such as tert-butyl isocyanide, including ligand exchange reactions and a surprising formation of white phosphorus. A milestone is the transformation of a nonmetal-bound isocyanide into phosphaguanidine or an acyclic bisaminocarbene bound to phosphorus; the latter is analogous to the chemistry of transition metal-bound isocyanides, and the former reveals the differences. This example has been studied via cutting-edge DFT calculations leading to two pathways differently favored depending on variations in steric demand. This study reveals the emergence of organometallic from coordination chemistry of a neutral nonmetal center.
RESUMEN
Phospha-Wittig reagents such as phosphanylidene-phosphoranes and their transition metal complexes are of great interest as sources of P1 building blocks but the access is still limited. Herein, we describe a new access to phosphanylidene-phosphorane complexes starting from the N-methylimidazole-to-phosphinidene complex adduct. The complexes were studied electrochemically and theoretically, also with respect to their 31P NMR data, and the P-P bonds were evaluated by various DFT-derived descriptors.
RESUMEN
Despite debate on intramolecular NâP interactions in peri-substituted naphthalene derivatives their coordination chemistry has not yet been reported. Herein, we describe bonding in and reactivity of dichloro(8-dimethylamino-1-naphthyl)phosphane towards pentacarbonyltungsten(0) reagents. A 1-aza-2-phospha-acenaphthene complex was obtained via the unexpected elimination of chloromethane enabled through P-coordination. Theoretical DFT calculations provide insights into Pâ¯N pnictogen bonding interaction as well as the reaction pathway of the elimination reaction.
RESUMEN
P-Functional phosphanylated tetrathiafulvalenes 3a-f were synthesised via stepwise lithiation and phosphanylation of TTF derivatives, and then reacted with PCl3 to form the related P-chloro compounds 4a-f. Reactions of 4c-f with LDA resulted in the formation of the corresponding 1,4-dihydro-1,4-diphosphinines 5c-f. As a case in point, P-oxidation reactions of 5d,f with elemental chalcogens were performed, and the former were also converted into 1,4-dichloro-1,4-dihydro-1,4-diphosphinine 9f. The latter was reduced to form the related 1,4-diphosphinine 10f which could not be isolated but formed the corresponding 1,4-diphosphabarrelene 11f in a [4 + 2]-cycloaddition with 1-hexene. All compounds were characterised by multinuclear NMR spectroscopy and mass spectrometry and also by single crystal X-ray diffraction studies in some cases. Intensive cyclic voltammetry studies were performed for all isolated compounds with the special focus on using TTF units as sensors to study the substituent effects on oxidation potentials and, hence, the degree of electronic communication between redox active moieties in the bis-TTF species. E.g., 5d possesses four quasi-reversible one-electron oxidation steps thus forming a tetracation species at highest potential (+0.54 V vs. Fc+/0). Additionally, high level DFT calculations were undertaken to get a deeper understanding of various aspects of this novel combination of phosphorus and TTF chemistry.
RESUMEN
Tricyclic 1,4-dihydro-1,4-phosphasilines 3a,b were synthesized from Si(NR2)2-bridged imidazole-2-thione compounds 2a,b. Based on calculated FMOs of 3b, forecasting a possible P-selective P-N bond cleavage reduction, a redox cycle could be established using solutions of P-centred anionic derivative K[4b]. The cycle started with the oxidation of the latter to give the P-P coupled product 5b which could be chemically reduced by KC8 to yield K[4b], again. All new products have been unambiguously confirmed in solution and solid state.
RESUMEN
Reaction of a transiently formed terminal phosphinidene complex with triethylamine resulted in the formation of an sp3 C-H insertion product, as revealed by 31P NMR spectroscopy, which was isolated as semi-solid compound. However, if the reaction was continued for 24 h, a primary phosphane complex was obtained eventually. The compounds were characterised by NMR spectroscopy and mass spectrometry. Formation of the final products is explained by a mechanistic proposal based on DFT calculations.
RESUMEN
Recently, we have synthesized phosphane W(CO)5 complexes containing a P-O-TEMP ligand motif as bench-stable precursors of thermally accessible phosphanoxyl complex radicals possessing a ligand with a P-OË group. In this work, extensive dispersion-corrected DFT calculations are used to explore both W(CO)5 and Fe(CO)4 phosphane complexes containing the P-E-TEMP ligands (E = O, S, NMe, and PMe) in order to reach thermally accessible radicals with a P-EË motif. Moreover, a more general single-electron transfer (SET) oxidation approach to synthesize such P-EË radicals via anionic precursors is disclosed. Furthermore, the tendencies for self-trapping and prototropic reactions of such radical complexes have been studied for the first time. Electronic structures and potential conversions of such P-EË radicals are discussed, thus paving the way to a broad range of transition metal radical complexes, including potential thermal radical initiators.
RESUMEN
After more than 160 years of oxirane (epoxide) chemistry, the first derivative of a phosphorus analogue, namely oxaphosphirane, has been synthesized. Reactions with borane sulfane, a peroxy compound and elemental sulfur, as well as tetra-chloro-ortho-benzoquinone (TOB) reveal a significant destabilization upon increasing the coordination number at phosphorus from σ3 to σ4, thus somehow supporting previous reports on such fleeting species. Theoretical studies provide insight into ring strain energy, ring/ring interconversion and the oxidation pathways.
RESUMEN
Extensive DFT calculations show that BH3NH3 may transfer dihydrogen as separated hydride and proton to CO2 rather than HCO3- in water over a barrier of 25.9 kcal mol-1, followed by faster hydride transfer from borate anions to either electrophilic CO2 or protic H2O or HCO2H, leading to competitive formate production and H2 release.
RESUMEN
This feature article highlights the discovery and development of phosphanoxyl complex chemistry starting from (neutral) low-coordinate phosphorus radicals and the quest of metal ligation effects. We describe synthesis and reactions of precursors, namely 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) substituted phosphane tungsten(0) complexes. Trapping reactions of transient phosphanoxyl complexes, formed via thermal homolytic N-O bond cleavage, as well as their use in radical polymerisations are illustrated, thus revealing an interesting reactivity dichotomy. DFT calculations provide insight into thermal stabilities of precursors and the resulting spin density distributions (SDDs) in these reactive intermediates. Systematic studies on the dependance of the electron delocalisation in phosphanoxyl complexes have been performed examining different substitution pattern at phosphorus and different co-ligand combinations at the tungsten(0) center. Preliminary results on Mn and Fe complexes are reported.