Medium‐sized phosphorus cluster cations P+2m+1 (6 ≤ m ≤ 32) studied by collision‐induced dissociation mass spectrometry

Medium‐sized phosphorus cluster cations were generated by laser ablation of red phosphorus and investigated by the method of collision‐induced dissociation mass spectrometry. Experimental results show that the primary dissociation channels of phosphorus cluster cations of P ⁺ _2m+1 (6 ≤ m ≤ 11) are all characterized by the loss of P₄ unit. For larger cluster cations, their dissociation pathways were more complex. For those magic cations of P ⁺ _8k+1 observed previously, their dissociation pathways progressively change from the loss of P₄ unit (for k = 3) to the loss of P₈ unit (for k = 4, 5). A new dissociation pathway characterized by the loss of P₁₀ unit was also indentified for larger cations of P ⁺ _8k+1 (6 ≤ k ≤ 8). Theoretical calculation also shows that, for cations of P ⁺ _2m+1 (4 ≤ m ≤ 10), the dissociation channel characterized by the loss of P₄ unit is more energetically favorable than other dissociation channels, which is in good agreement with the experimental results. Copyright © 2015 John Wiley & Sons, Ltd.     

Electrooxidation of 2,3-dihydro-1H-1,3,2-diazaphospholes

Electrooxidation of 2-R-1,3-dibutyl-4,5-dimethyl-2,3-dihydro-1H-1,3,2-diazaphospholes with tri- and tetracoordinated phosphorus atoms were studied. Reversible one-electron oxidation gives radical cations at potentials of −0.37 to +0.36 V. Magnetic parameters of the radical cations were measured. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1522–1524, August, 1998.     

Theoretical and X-Ray Evidence of Electrostatic Phosphonium anti and gauche Effects

Sulphur, not phosphorus, is the only known third-row element capable of experiencing an electrostatic gauche effect with fluorine. Some six-membered rings containing an endocyclic phosphorus atom and a β-fluorine substituent that can interconvert to axial (gauche relative to phosphorus) and equatorial positions were then analysed. While phosphines do not establish an electrostatic attraction between fluorine and phosphorus, some oxidised forms exhibit surprising stability for the sterically disfavoured axial orientation. Because the nature of this behaviour was not obvious, since an intramolecular hydrogen bond can appear, a phosphonium derivative was further studied and its axial conformation was found to be highly stable. A preference for the gauche arrangement appears even for the acyclic and sterically hindered (2-fluoroethyl)triphenylphosphonium cation. On the other hand, (ethane-1,2-diyl)bis(phosphonium) cations are exclusively in anti conformation due to an (+/+)-electrostatic repulsion between the positively charged phosphonium groups.     

Interaction of Donors with Electron Deficient Low-Coordinated Phosphorus Compounds

Mono-and bis-donor-acceptor formation (donor=AH₃, Y = N, P, As, Sb, Bi and AH₂, O, S, Se, Te) is discussed on the basis of quantum chemical (ab initio) calculations for π-bonded low-coordinated phosphorus cations, evaluating new types of bis-donor adducts.     

Elucidation of the Reaction Products of Acetonitrile with Phosphorus Pentachloride

Abstract

The reaction of acetonitrile with PCl, results in the ionic compounds (1) to (4) containing the trichloro[2-chloro-2-[(trichlorophosphoranyli-dene)amino]ethenyl]phosphorus cations and not in the compounds [CH2?C?NPCl₃]PCl₆1 or trichloro[2-chloro-1 -[(trichlorophosphoranyli-dene)amino] ethenyl]phosphorus hexachlorophosphate (5) as assumed from ³¹P-NMR spectra [2, 3]. The crystal structures of the compounds (1) to (4) were determined with X-rays at 95K. As observed for the CI-C(NPCl₃); cation all the cations show cis-trans conformations with respect to their CI-C-X-P torsion angles. The wcl3 groups of the cations have two different orientations with one C?N?P?CI torsion angle of about 0° (cis) as in (1) or about 180° (trans) as in (3) and (4). In the salt (2) there are two formula units in the asymmetric unit with one cation showing the cis and the other showing the tram conformation.     

Ylide-Stabilized Phosphenium Cations: Impact of the Substitution Pattern on the Coordination Chemistry

Although N-heterocyclic phosphenium (NHP) cations have received considerable research interest due to their application in organocatalysis, including asymmetric synthesis, phosphenium cations with other substitution patterns have hardly been explored. Herein, the preparation of a series of ylide-substituted cations of type [YPR]⁺ (with Y=Ph₃PC(Ph), R=Ph, Cy or Y) and their structural and coordination properties are reported. Although the diylide-substituted cation forms spontaneous from the chlorophosphine precursor, the monoylidylphosphenium ions required the addition of a halide-abstraction reagent. The molecular structures of the cations reflected the different degrees of electron donation from the ylide to the phosphorus center depending on the second substituent. Molecular orbital analysis confirmed the stronger donor properties of the ylide systems compared to NHPs with the mono-ylide substituted cations featuring a more pronounced electrophilicity. This was mirrored by the reaction of the cations towards gold chloride, in which only the diylide-substituted cation [Y₂P]⁺ formed the expected LAuCl]⁺ complex, while the monoylide-substituted compounds reacted to the chlorophosphine ligands by transfer of the chloride from gold to the phosphorus center. These results demonstrate the tunability of ylide-functionalized phosphorus cations, which should allow for further applications in coordination chemistry in the future.     

KCo(H2O)2BP2O8·0.48H2O and K0.17Ca0.42Co(H2O)2BP2O8·H2O: two cobalt borophosphates with helical ribbons and disordered (K,Ca)/H2O schemes

The two title compounds, potassium diaquacobalt(II) borodiphosphate 0.48‐hydrate and potassium–calcium(0.172/0.418) diaquacobalt(II) borodiphosphate monohydrate, were synthesized hydrothermally. They are new members of the borophosphate family characterized by _∞[BP₂O₈]³⁻ helices running along [001] and constructed of boron (Wyckoff position 6b, twofold axis) and phosphorus tetrahedra. The [CoBP₂O₈]⁻ anionic frameworks in the two materials are structurally similar and result from a connection in the ab plane between the CoO₄(H₂O)₂ coordination octahedra (6b position) and the helical ribbons. Nevertheless, the two structures differ in the disorder schemes of the K,Ca and H₂O species. The alkali cations in the structure of the pure potassium compound are disordered over three independent positions, one of them located on a 6b site. Its framework is characterized by double occupation of the tunnels by water molecules located on twofold rotation axes (6b) and a fraction of alkali cations; its cell parameters, compared with those for the mixed K,Ca compound, show abnormal changes, presumably due to the disorder. For the K,Ca compound, the K and Ca cations are on twofold axes (6b) and the channels are occupied only by disordered solvent water molecules. This shows that it is possible, due to the flexibility of the helices, to replace the alkali and alkaline earth cations while retaining the crystal framework.     

Theoretical calculations of nuclear spin coupling of phosphorus to carbon and hydrogen by the finite perturbation method

Finite perturbation calculations using CNDO/2 wave functions are presented for the determination of ³¹P? ¹³C and ³¹P? ¹H couplings. The calculations were carried out on 46 molecules and a comparison with experimental values is given. The groups of compounds considered were phosphonium cations, phosphine oxides, alkylidenephosphoranes, phosphine sulfides, phosphoranes and phosphines. With the exception of phosphines, the finite perturbation approach reproduces the experimental couplings with fair accuracy. It is found that there is a good correlation with the calculated ¹J(P, C) and the phosphorus 3s-carbon 2s bond orders for tetra- and pentavalent phosphorus compounds. This lends support to the growing body of evidence for the direct relationship of the magnitude of ¹J(P, C) and percent s character in the hybrid orbital on the carbon comprising the P? C bond. The finite perturbation technique was also used to explore the effects of geometrical changes on P? C and P? H couplings. Finally, the effect of deleting d orbitals on phosphorus is discussed briefly.     

RE4[P1–x(C2)x]3 (RE = La–Nd): the Mixed Anionic Substructure Formed by Phosphorus and Carbon

The rare‐earth phosphide carbides RE₄[P_1–x(C₂)_x]₃ (RE = La, Ce, Pr, Nd) represent the first example of a mixed anionic substructure formed by phosphorus and carbon, being the first step toward the formation of the mixed inorganic P–C species. The peculiarities of the crystal structure, magnetic properties, XAS data, and quantum chemical calculation results confirm the ionic nature of the interaction between the rare‐earth cations RE and phosphorus anions, while complex interaction of π states of the C₂ anions and d (and/or f) states of the RE components is indicated. Thus, despite the extensive chemical analogy between the phosphide carbides and phosphide silicides, the atomic interactions stabilizing the structural motif are slightly different.     

铁、钴、镍/磷二元团簇离子的形成与光解

利用激光直接溅射法产生了铁、钴、镍／磷二元团簇正负离子,并用串级飞行时间质谱仪研究了团族离子的组份和激光光解规律,质谱研究表明,铁、钴、镍易与磷结合成簇,而且样品中磷含量的增加有助于大尺寸团簇离子的生成,当形成的团族簇离子中含金属原子数目较少时,磷原子数目可在较大范围内变动,其中ＭＰ２＾＋、ＭＰ４＾＋、Ｍ２Ｐ４＾＋（Ｍ＝Ｆｅ、Ｃｏ、Ｎｉ,ｎ＝２、３、４）团簇离子均具有较高的丰度;随着金属原子数目的     

On the electronic structure of dihalogenophosphenium cations

The bonding properties of the dihalogenophosphenium cations, PX₂⁽⁺⁾, X = F, Cl, Br, I, are evaluated by relativistic effective core potential calculations with a DZP basis set. Our investigations include an analysis of the singlet-triplet energy separation in the cations and the determination of the relative cation and anion stabilities in the gas phase, via corresponding group transfer reactions. A comparison is made with other stabilized, previously reported low-coordinated π-bonded phosphorus cations.     

团簇尺寸对奇数和偶数磷团簇离子信号强度差异的影响

磷原子形成的奇数和偶数团簇离子的信号存在明显的强度差异. 当团簇离子尺寸n>25时, 奇数团簇离子的信号强度一般会远远超过其邻近的偶数团簇离子. 为更好地理解团簇尺寸对这一现象的影响, 本文通过真空中激光溅射红磷的方法, 利用质谱对磷团簇离子进行了研究和分析. 结果表明这种方法可以产生较大尺寸(n~500)的磷团簇离子. 进一步对团簇离子的强度分布进行分析表明: 随着正负离子团簇尺寸的增加, 奇/偶数离子强度差异都会逐渐减小. 根据它们的变化趋势, 可以预测: 当n>1000时, 奇/偶数离子强度交替的现象可能会消失. 这一结果正反映出团簇在从原子演变到凝聚态物质过程中的桥梁作用.     

Methylpyrazine Ammoxidation over Binary Oxide Systems: V. Effect of Phosphorus Additives on the Physicochemical and Catalytic Properties of a Vanadium–Titanium Catalyst in Methylpyrazine Ammoxidation

Oxide vanadium–titanium catalysts modified by phosphorus additives (20V₂O₅–(80 –n)TiO₂–nP₂O₅, n = 1, 3, 5, 10, and 15 wt %) are studied in methylpyrazine ammoxidation. Two regions of compositions are found corresponding to radically different catalytic properties, namely, catalysts with a low (5 wt % P₂O₅) and high (10 wt % P₂O₅) concentration of the additive. In the first case, the introduction of phosphorus is accompanied by a gradual increase in the activity. In the second case, an increase in the additive concentration results in a decrease in the activity and selectivity to the target product, pyrazineamide, and a simultaneous increase in the selectivities to by-products, pyrazine and carbon oxides. The catalysts are characterized by X-ray diffraction analysis, differential dissolution, IR, and NMR spectroscopic data. As in the binary system, the active sites of the samples with a low concentration of phosphorus contain V⁵⁺ cations in a strongly distorted octahedral oxygen environment, which are strongly bound to a support due to the formation of V–O–Ti bonds. The catalytic properties of the samples containing 10 wt % P₂O₅ are due to the presence of the phase of a triple V–P–Ti compound with an atomic ratio V : P : Ti approximately equal to 1 : 1 : 1. The V⁵⁺ cations in this compound occur in a weakly distorted tetrahedral oxygen environment and are bound to the tetrahedral P⁵⁺ cations.     

Structure of Low-Coordinated Phosphorus (III) Compounds Including Phosphorus-Nitrogen Multiple Bond: 13C, 15N and 31P NMR Investigation

Abstract

A wide series of low-coordinated phosphorus (III) compounds including iminophosphines 1, two- 2 or mono-coordinated 3 phosphorus-containing cations, and anion 4, where Mes? = 2,4,6-tris-(tert-butyl)phenyl, has been investigated by ¹³C, ¹⁵N and ³¹P NMR spectroscopy. The spectral parameters obtained are considered in connection with the ab initio (6–31G?) calculation data of the model compounds.     

Polyimido Sulfur(VI) Phosphanyl Ligand in Metal Complexation

Herein, new complexes containing the [Ph₂PCH₂S(NtBu)₃]^? anion are presented, supplying three imido nitrogen atoms and a remote phosphorus atom as potential donor sites to main group and transition‐metal cations. The lithiated complex [(tmeda)Li{(NtBu)₃SCH₂PPh₂}] ( 1 ) is an excellent starting material in transmetalation reactions. Herein, the transition‐metal complexes [M{(NtBu)₃SCH₂PPh₂}₂] (M=Mn ( 2 ), Ni ( 3 ), Zn ( 4 )) were synthesized and structurally characterized. Their isotypical molecules show SN₂ chelation and no employment of the adjacent phosphorus atom in coordination. The third pendent imido group is always twisted toward the vacant face of the tetrahedrally coordinated sulfur atom.     

Complexes of 2,2′,2″-Nirtilotriphenol. Part IV. Cage Compounds with Phosphorus(III) and Phosphorus(V)

The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite ( II ), 2,2′,2″-nitrilotriphenyl phosphate ( III ) and of a hydrolysis product of II , 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate ( IV ), are reported, as well as crystal structures of II and IV . Phosphite II shows a bicycloundecane framework; no N?Pinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.     

Coordination Chemistry of Cyclopropenylidene‐Stabilized Phosphenium Cations: Synthesis and Reactivity of Pd and Pt Complexes

A straightforward synthesis of cyclopropenylidene‐stabilized phosphenium cations 1 a – g through the reaction of [(iPr₂N)₂C₃⁺Cl]BF₄ with secondary phosphines is described. Their donor ability was evaluated by analysis of the CO stretching frequency in Rh complexes [RhCl(CO)L₂](BF₄)₂ and electrochemical methods. The cyclopropenium ring induces a phosphite‐type behavior that can be tuned by the other two substituents attached to the phosphorus atom. Despite of the positive charge that they bear, phosphenium cations 1 a – g still act as two‐electron donor ligands, forming adducts with Pd^II and Pt^II precursors. Conversely, in the presence of Pd⁰ species, an oxidative insertion of the Pd atom into the C_carbene–phosphorus bond takes place, providing dimeric structures in which each Pd atom is bonded to a cyclopropenyl carbene while two dialkyl/diaryl phosphide ligands serve as bridges between the two Pd centers. The catalytic performance of the resulting library of Pt^II complexes was tested; all of the cationic phosphines accelerated the prototype 6‐endo‐dig cyclization of 2‐ethynyl‐1,1′‐biphenyl to afford pentahelicene. The best ligand 1 g was used in the synthesis of two natural products, chrysotoxene and epimedoicarisoside A.     

A Delamination Strategy for Thinly Layered Defect‐Free High‐Mobility Black Phosphorus Flakes

Extraordinary electronic and photonic features render black phosphorus (BP) an important material for the development of novel electronics and optoelectronics. Despite recent progress in the preparation of thinly layered BP flakes, scalable synthesis of large‐size, pristine BP flakes remains a major challenge. An electrochemical delamination strategy is demonstrated that involves intercalation of diverse cations in non‐aqueous electrolytes, thereby peeling off bulk BP crystals into defect‐free flakes comprising only a few layers. The interplay between tetra‐n‐butylammonium cations and bisulfate anions promotes a high exfoliation yield up to 78 % and large BP flakes up to 20.6 μm. Bottom‐gate and bottom‐contact field‐effect transistors, comprising single BP flakes only a few layers thick, exhibit a high hole mobility of 252±18 cm² V^?1 s^?1 and a remarkable on/off ratio of (1.2±0.15)×10⁵ at 143 K under vacuum. This efficient and scalable delamination method holds great promise for development of BP‐based composites and optoelectronic devices.     

peri-Interactions in Naphthalenes, 15: The Concept of Incipient Bipyramidalization in 8-Dimethylaminonaphth-1-yl Silanes and Phosphonium Cations

The concept of a gradual transition from tetracovalent to hypercoordinated silicon and phosphorus in 8-dimethylamino-naphth-1-yl silanes and phosphonium cations is critically examined. Various procedures to quantify partial bipyramidalization fail to indicate incipient hypercoordination. In particular, deviations from tetrahedrality in trialkyl-(8-dimethylamino-naphth-1-yl) silanes and tri(alkyl/phenyl)-(8-dimethylamino-naphth-1-yl) phosphonium cations do not reflect weak N → Si/P bonding. Likewise, the distortions at the P⁺ center in tri(alkyl/phenyl)-(8-diphenylphosphino-naphth-1-yl) phosphonium cations are not indicative of dative P → P⁺ interactions.