On Haptotropic Rearrangements of Diphosphene and Diarsene Ligands in Titanium Complexes.

Dipnictenes of the type RE=ER (E=P, As, Sb, Bi) are the isovalence electronic heavier analogs of alkenes. Although diphosphenes and dipnictenes in general show a variety of binding modes in metal complexes, little is known about haptotropic shift reactions involving these ligands. Herein, we report an unprecedented η2 to η1 rearrangement of the dipnictene ligands in titanocene complexes of the type Cp2Ti(Pn2Ar2) (Pn=P, As; Ar=2,4,6-Me3-C6H2, Mes; 2,6-iPr2-C6H3, Dip; 2,4,6-iPr3-C6H2, Tip), initiated by Lewis basic ligands (L=MeCN, PMe3, AdNC, CO). In the presence of L the dipnictene ligand changes its hapticity from η2 to η1 and complexes of the general form Cp2Ti(L)(Pn2Ar2) with a succinctly different electronic structure are obtained. Electronically, the new complexes are best described as biradicaloids with antiferromagnetically coupled (via a π-bond) [Cp2TiIII]⋅+ and [Pn2Ar2]⋅- fragments. However, the biradical character of these systems is affected by the electronic features of the co-ligand and significantly decreases moving from PMe3/MeCN (σ-donors) to CNAd/CO (σ-donors/π-acceptors).

Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation.

Highly selective rare-earth separation has become increasingly important due to the indispensable role of these elements in various cutting-edge technologies including clean energy. However, the similar physicochemical properties of rare-earth elements (REEs) render their separation very challenging, and the development of new selective receptors for these elements is potentially of very considerable economic and environmental importance. Herein, we report the development of a series of 4-phosphoryl pyrazolone receptors for the selective separation of trivalent lanthanum, europium, and ytterbium as the representatives of light, middle, and heavy REEs, respectively. X-ray crystallography studies were employed to obtain solid-state structures across 11 of the resulting complexes, allowing comparative structure-function relationships to be probed, including the effect of lanthanide contraction that occurs along the series from lanthanum to europium to ytterbium and which potentially provides a basis for REE ion separation. In addition, the influence of ligand structure and lipophilicity on lanthanide binding and selectivity was systematically investigated via n-octanol/water distribution and liquid-liquid extraction (LLE) studies. Corresponding stoichiometry relationships between solid and solution states were well established using slope analyses. The results provide new insights into some fundamental lanthanide coordination chemistry from a separation perspective and establish 4-phosphoryl pyrazolone derivatives as potential practical extraction reagents for the selective separation of REEs in the future.

4-Phosphoryl Pyrazolones for Highly Selective Lithium Separation from Alkali Metal Ions.

Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, HL2 -HL4 , in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for HL4 compared to the use of the industrially employed acylpyrazolone HL1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+ , K+ and Cs+ under mild conditions (pH ∼8.2) confirms that HL2 -HL4 represent a new class of ligands that are very effective extractants for use in lithium separation.

Saccharified Uranyl Ions: Self-Assembly of UO2 2+ into Trinuclear Anionic Complexes by the Coordination of Glucosamine-Derived Schiff Bases.

The reaction of UO2 (OAc)2 ⋅ 2H2 O with the biologically inspired ligand 2-salicylidene glucosamine (H2 L1 ) results in the formation of the anionic trinuclear uranyl complex [(UO2 )3 (µ3 -O)(L1 )3 ]2- (12- ), which was isolated in good yield as its Cs-salt, [Cs]2 1. Recrystallization of [Cs]2 1 in the presence of 18-crown-6 led to formation of a neutral ion pair of type [M(18-crown-6)]2 1, which was also obtained for the alkali metal ions Rb+ and K+ (M=Cs, Rb, K). The related ligand, 2-(2-hydroxy-1-naphthylidene) glucosamine (H2 L2 ) in a similar procedure with Cs+ gave the corresponding complex [Cs(18-crown-6)]2 [(UO2 )3 (µ3 -O)(L2 )3 ([Cs(18-crown-6)]2 2). From X-ray investigations, the [(UO2 )3 O(Ln )3 ]2- anion (n=1, 2) in each complex is a discrete trinuclear uranyl species that coordinates to the alkali metal ion via three uranyl oxygen atoms. The coordination behavior of H2 L1 and H2 L2 towards UO2 2+ was investigated by NMR, UV/Vis spectroscopy and mass spectrometry, revealing the in situ formation of the 12- and 22- dianions in solution.

Polymorphic Phosphorescence from Separable Aggregates with Unique Photophysical Properties.

Platinum complexes aggregate into polymorphs with different intermolecular interactions leading to different photophysical properties. Strong intermolecular interactions stabilize the aggregate to such an extent that the polymorphs can be separated directly by column chromatography. Solid-state structures as well as quantum-chemical calculations confirmed the effect of the interactions on the photophysical properties.

Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO2 Sequestration and Binding of Carbonyls, Nitriles and Acetylenes.

Electrophilic fluorophosphonium triflates bearing pyridyl (3[OTf]) or imidazolyl (4[OTf])-substituents act as intramolecular frustrated Lewis pairs (FLPs) and reversibly form 1 : 1 adducts with CO2 (5+ and 6+ ). An unusual and labile spirocyclic tetrahedral intermediate (72+ ) is observed in CO2 -pressurized (0.5-2.0 bar) solutions of cation 4+ at low temperatures, as demonstrated by variable-temperature NMR studies, which were confirmed crystallographically. In addition, cations 3+ and 4+ actively bind carbonyls, nitriles and acetylenes by 1,3-dipolar cycloaddition, as shown by selected examples.

Coordination Chemistry and Methylation of Mixed-Substituted Tetraphosphetanes (RP-PtBu)2 (R=Ph, Py).

Synthesis of mixed-substituted tetraphosphetanes (RP-PtBu)2 (R=Ph (4), Py (5); Py=2-pyridyl) is achieved from the condensation of dipyrazolylphosphanes RPpyr2 (R=Py (1), Ph (3); pyr=3,5-dimethylpyrazolyl) as P1 -building block (R-P) and tBuPH2 in an equimolar ratio. Compound 5 is of special interest since the presence of two pyridyl-substituents as well as the P4 -core allows for a rich coordination chemistry with coinage metal salts [Cu(MeCN)4 ][OTf], Ag[OTf] and in situ formed [Au(tht)][OTf] (tht=tetrahydrothiophene). Both tetraphosphetanes undergo alkylation reaction with MeOTf to give a series of tetraphosphetanium and tetraphosphetanediium triflate salts with additional methylation of the pyridyl-moiety in case of 5 resulting in interesting novel cyclic trications. Harsh reaction condition and an excess of MeOTf converts 5 into the cyclic trication [-P(Me Py)PMe2 P(Me Py)PtBu-]3+ (133+ ; Me Py=1-methylpyridiniumyl) through the elimination of isobutene. This salt undergoes a complicated rearrangement reaction involving a P-P/P-P bond metathesis to form trication [-P(MePy)3 PtBu-]3+ (173+ ) when reacted with Me2 PPMe2 .

Coordination Chemistry and Methylation of Mixed-Substituted Tetraphosphetanes (RP-PtBu)2 (R=Ph, Py).

Invited for the cover of this issue is the group of Jan J. Weigand at Technische Universität Dresden. The image depicts a puzzle illustrating the coinage metal cations and the methyl group, from which the three-dimensional structure of a multiply methylated tetraphosphetane arises. Read the full text of the article at 10.1002/chem.202001360.

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts.

A novel method for the one-pot synthesis of diannulated 1,4,2-diazaphospholium triflate salts by a Me3SiOTf-mediated self-condensation of dichlorophosphaneyl aza-(poly)cyclic aromatic hydrocarbons (aza-(P)AHs; namely, pyridine, quinoline, phenanthridine, and benzo[d]thiazole) is reported. The diannulated 1,4,2-diazaphospholium triflate salts are characterized by multinuclear NMR spectroscopy, X-ray analysis, as well as their calculated NICS values, underlining their aromatic character. Quantum mechanical calculations shed light on the intermolecular reaction mechanism. Follow up chemistry, such as the halogenation reaction with XeF2 or SO2Cl2 with the dipyridinium derivative selectively yields the respective dihalo-σ4,λ5- and tetrahalo-σ5,λ6-diazaphospholium triflate salts. The dihalo-σ4,λ5-diazaphospholium triflate salt serves well as a surrogate for the introduction of the cationic 2-(1,2'-bipyridin)-1-iumyl ligand (1,2'-bipyl), the monocationic structural isomer of the prototypical 2,2'-bipyridine ligand (2,2'-bipy).

P-P Condensation and P-N/P-P Bond Metathesis: Facile Synthesis of Cationic Tri- and Tetraphosphanes.

[LC R P((PhP)2 C2 H4 )][OTf] (4 a,b[OTf]) and [LC iPr P(PPh2 )2 ][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [LC R P(pyr)2 ][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; LC R =1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C2 H4 P(H)Ph) and Ph2 PH. A stepwise double P-N/P-P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph2 P)2 (LC Me P)2 ][OTf]2 (7 a[OTf]2 ) is observed when reacting 3 a[OTf] with diphosphane P2 Ph4 . The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH3 CN)4 ]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph2 PPLC iPr )Au}4 ][OTf]4 (9[OTf]4 ) was unexpectedly formed as a result of a chloride-induced P-P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH3 CN)3 ][OTf]2 (M=Cu, Ag) (10[OTf]2 , 11[OTf]2 ).

Helical Nanographenes Containing an Azulene Unit: Synthesis, Crystal Structures, and Properties.

Three unprecedented helical nanographenes (1, 2, and 3) containing an azulene unit are synthesized. The resultant helical structures are unambiguously confirmed by X-ray crystallographic analysis. The embedded azulene unit in 2 possesses a record-high twisting degree (16.1°) as a result of the contiguous steric repulsion at the helical inner rim. Structural analysis in combination with theoretical calculations reveals that these helical nanographenes manifest a global aromatic structure, while the inner azulene unit exhibits weak antiaromatic character. Furthermore, UV/Vis-spectral measurements reveal that superhelicenes 2 and 3 possess narrow energy gaps (2: 1.88 eV; 3: 2.03 eV), as corroborated by cyclic voltammetry and supported by density functional theory (DFT) calculations. The stable oxidized and reduced states of 2 and 3 are characterized by in-situ EPR/Vis-NIR spectroelectrochemistry. Our study provides a novel synthetic strategy for helical nanographenes containing azulene units as well as their associated structures and physical properties.

Toward Full Zigzag-Edged Nanographenes: peri-Tetracene and Its Corresponding Circumanthracene.

Zigzag-edged nanographene with two rows of fused linear acenes, called as n- peri-acene (n-PA), is considered as a potential building unit in the arena of organic electronics. n-PAs with four ( peri-tetracene, 4-PA), five ( peri-pentacene, 5-PA) or more benzene rings in a row have been predicted to show open-shell character, which would be attractive for the development of unprecedented molecular spintronics. However, solution-based synthesis of open-shell n-PA has thus far not been successful because of the poor chemical stability. Herein we demonstrated the synthesis and characterization of the hitherto unknown 4-PA by a rational strategy in which steric protection of the zigzag edges playing a pivotal role. The obtained 4-PA possesses a singlet biradical character ( y0 = 72%) and exhibits remarkable persistent stability with a half-life time ( t1/2) of ∼3 h under ambient conditions. UV-vis-NIR and electrochemical measurements reveal a narrow optical/electrochemical energy gap (1.11 eV) for 4-PA. Moreover, the bay regions of 4-PA enable the efficient 2-fold Diels-Alder reaction, yielding a novel full zigzag-edged circumanthracene.

Exploration of Thiazolo[5,4-d]thiazole Linkages in Conjugated Porous Organic Polymers for Chemoselective Molecular Sieving.

Porous organic polymers (POPs) have attracted significant attention towards molecular adsorption in recent years due to their high porosity, diverse functionality and excellent chemical stability. In this work, we present a systematic case study on the formation of thiazolo[5,4-d]thiazole (TzTz) linkages through model compounds and its integration to synthesize a set of three novel, thermo-chemically stable TzTz-linked POPs, namely TzTz-POP-3, TzTz-POP-4, and TzTz-POP-5 with triphenylbenzene, tetraphenylpyrene and tetra(hydroxyphenyl)methane cores, respectively. Interestingly, the integrated TzTz moiety of the represented TzTz-POP-3 renders chemoselective removal of organic dye fluorescein (FL) from a mixture with parafuchsine (FU) in aqueous solution. The TzTz-POP-3 offered excellent chemoselectivity of ≈1:7 (FL:FU), compared to alike porous materials demonstrated for similar applications due to the presence of multiple active anchoring sites coupled with permanent porosity and appropriate pore window.

Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus.

The reaction of LGa (L = Dipp(4-(Dipp-imino)pent-2-en-2-yl)amide; Dipp: 2,6-diisopropylphenyl) and white phosphorus was revisited. A plethora of unprecedented polyphosphanes in addition to the known monoinserted product LGaP4 (1) are observed. An optimized synthesis of the hitherto unknown hexaphosphane (LGa)2P6 (3) is presented, and its subsequent selective derivatization with Brønsted acids, MeOTf, Ph2ECl (E = P, As), and NaOCP provides access to a wealth of functionalized hexa- and heptaphosphanes.

π-Extended and Curved Antiaromatic Polycyclic Hydrocarbons.

Synthesis of antiaromatic polycyclic hydrocarbons (PHs) is challenging because the high energy of their highest occupied molecular orbital and low energy of their lowest unoccupied molecular orbital cause them to be reactive and unstable. In this work, two large antiaromatic acene analogues, namely, cyclopenta[pqr]indeno[2,1,7-ijk]tetraphene (CIT, 1a) and cyclopenta[pqr]indeno[7,1,2-cde]picene (CIP, 1b), as well as a curved antiaromatic molecule with 48 π-electrons, dibenzo[a,c]diindeno[7,1,2-fgh:7',1',2'-mno]phenanthro[9,10-k]tetraphene (DPT, 1c), are synthesized on the basis of the corona of indeno[1,2-b]fluorene. These three antiaromatic PHs possess a narrow energy gap down to 1.55 eV and exhibit high kinetic stability under ambient conditions. Moreover, these compounds display reversible electron transfer processes in both the cathodic and anodic regimes. Their cation and anion radicals are characterized by in situ vis-NIR absorption and electron paramagnetic resonance spectroelectrochemistry. The X-ray crystallographic analysis confirms that while CIP and CIT manifest planar structures, DPT shows a curved π-conjugated carbon skeleton. The synthetic strategy starting from ortho-substituted benzene units to construct five-membered rings in this work provides a unique entry to novel pentagon-embedding or curved antiaromatic polycyclic hydrocarbons. In addition, besides the detailed chemical and physical investigations, microscale single-crystal fiber field-effect transistors were also fabricated.

Nitrogen-Phosphorus(III)-Chalcogen Macrocycles for the Synthesis of Polynuclear Silver(I) Sandwich Complexes.

The synthesis of inorganic N-P(III)-Ch-based macrocycles [-PhP-NMe-PPh-Ch-]2 (8Ch; Ch = S, Se) is presented by incorporating two nitrogen, two chalcogen, and four phosphorus atoms. The macrocycles are conveniently obtained via the cyclocondensation reaction of Na2Ch (Ch = S, Se) with the acyclic dichlorodiphosphazane ClPhP-NMe-PClPh (9). Treatment with elemental sulfur (S8) or gray selenium (Segray) results in an oxidative ring contraction to give 1,3,2,4-thiazadiphosphetidine 2,4-disulfide (10S) and 1,3,2,4-selenazadiphosphetidine 2,4-diselenide (10Se), respectively. Macrocycles 8Ch are excellent multidentate ligands for transition metal complexation, as demonstrated by the isolation of mono-, di- tri-, and tetranuclear silver sandwich complexes. The polynuclear silver complexes are comprehensively characterized, including detailed NMR and X-ray analysis.

Recent highlights in mixed-coordinate oligophosphorus chemistry.

This review aims to highlight and comprehensively summarize recent developments in the field of mixed-coordinate phosphorus chemistry. Particular attention is focused on the synthetic approaches to compounds containing at least two directly bonded phosphorus atoms in different coordination environments and their unexpected properties that are derived from spectroscopic and crystallographic data. Novel substance classes are discussed in order to supplement previous reviews about mixed-coordinate phosphorus compounds.

A Tetracyclic Octaphosphane by Successive Addition, Inversion, and Condensation Reactions.

An example of an octaphosphane of type R2 P8 (R=(DDP)Ga) was isolated by treatment of cage compound (DDP)GaP4 (2, DDP=(2,6-diisopropylphenyl)(4-((2,6-diisopropylphenyl)imino)pent-2-en-2-yl)amide) with (C6 F5 )2 PBr. The initially formed endo-exo butterfly shaped pentaphosphane 7 rapidly rearranges to the more stable exo-exo isomer 8, which undergoes dimerization to decaphosphane 11. Compound 11 unexpectedly eliminates tetraaryldiphosphane 13 to give tetracyclo[3.3.0.02,7 .04,6 ]octaphosphane [(DDP)GaBr]2 P8 (12). The reaction steps were confirmed by crystal structure analysis of the key intermediates and supported by kinetic studies using NMR techniques.

Isolation of Azadiphosphiridines and Diphosphenimines by Cycloaddition of Azides and a Cationic Diphosphene.

The polarized, cationic diphosphene [(Cl ImDipp )P=P(Dipp)]+ as the triflate salt 7[OTf](Cl ImDipp =4,5-dichloro-1,3-bis(Dipp)-imidazol-2-yl; Dipp=2,6-diisopropylphenyl) reacts with azides of type RN3 (R=Dipp or Dmp; Dmp=2,5-dimethylphenyl) in a [2+3] cycloaddition reaction followed by the release of N2 and a subsequent electrocyclic ring-closing reaction to azadiphosphiridine salts [(Cl ImDipp )P-P(Dipp)-N(R)]10a,b[OTf] (R=Dipp or Dmp). The reaction of 7[X] (X=OTf, GaCl4 ) with the electron-rich azides Me3 SiN3 and NaN3 give the unusual diphosphenimine derivatives [(Cl ImDipp )P-P(Dipp)=N(SiMe3 )]+ (11[OTf]) and [(Cl ImDipp )P-P(Dipp)=N(GaCl3 )] (12), respectively, featuring an acyclic P2 N moiety. Theoretical calculations provide insights into the reaction mechanisms to the cyclic and acyclic forms, in which the thermodynamic stability of the latter prevents the electrocyclic ring closure.

Selective and Reversible Fluoride Complexation from Water by a Cyclic Tri(phosphonio)methanide Dication.

Tri(phosphonio)methanide dication 32+ , prepared from a trifluoromethylsulfanylphosphonium dication (12+ ) via an intramolecular electrophilic aromatic substitution reaction, is an unexpected P-based, water-resistant Lewis acid that is capable to selectively and reversibly bind fluoride ions from organic/aqueous biphasic solution. The formed complex is an unusual fluorophosphorane ([3-F]OTf). The multiple donor-acceptor interactions of 32+ that are crucial for the fluoride fixation have been elucidated by quantum chemical calculation. Compound [3-F]OTf can also be used as a convenient anhydrous fluoride ion source and was probed as a suitable catalyst of the silylotrifluoromethylation of various aldehydes.