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We report a class of compounds in which both PIII−X and PI forms featuring the same ligand are stable and readily cycled with each other. A series of PIII−X (X=Cl, Br, I) dicationic triflate salts supported by benzyl‐ and allyl‐substituted 2,6‐bis(benzimidazole‐2‐yl)pyridine (BZIMPY) ligands is synthesized. Surprisingly, treatment of these with R3PO (R=Et, Oct) results in reduction to BZIMPY‐ligated PI monocationic triflate salts while treatment with Ph3P reduces but also substitutes the compound to produce Ph3P‐BZIMPY‐ligated PI dicationic triflate salts. The mechanisms of these surprising reductions are probed experimentally and rationalized computationally. The PIII−X dications are shown to be strong Lewis acids both experimentally and computationally and to readily behave as X+, PX, and P+ transfer agents in reactions with phosphines, NHCs, and diazabutadienes. The PI mono‐ and dications are shown to be very effective P+ transfer agents when treated similarly. Oxidation from a monocationic PI salt back to the dicationic PIII−X (X=Cl, Br) salt was achieved by treatment with N‐chlorosuccinimide (NCS) or N‐bromosuccinimide (NBS). Full characterization is reported using multinuclear nuclear magnetic resonance spectroscopy, elemental analysis, and single‐crystal X‐ray diffractometry where suitable crystals were isolated. [ABSTRACT FROM AUTHOR]

This study reports on the exploration of the phosphinoboration reaction with several thiosemicarbazones (R5R4NC(S)NR3N=CR1R2). Reactions between either Ph2PBpin (pin = 1,2-O2C2Me4) or Ph2PBcat (cat = 1,2-O2C6H4) with thiosemicarbazones containing a terminal primary or secondary amine afforded boron-containing heterocyclic 1,3,4-thiadiazoline products in excellent yield. The addition of Ph2PBpin to thiosemicarbazones containing an NMe2 group in the terminal position generated novel five-membered heterocycles in moderate yield, which included boron, sulfur, and nitrogen atoms. Heterocyclization of the thiosemicarbazones occurs preferentially in the presence of functional groups such as acetyl and pyridyl groups. [ABSTRACT FROM AUTHOR]

While cyanine dyes enjoy a multitude of uses in science and technology, their phosphorus analogues, phosphamethine cyanine dyes, have not yet found benchtop applications primarily because of their sensitivity to air and moisture. We are excited to report full characterization of an extraordinarily stable acyclic phosphamethine cyanine dye. Nitrile substituents on the N-heterocyclic framework afford air and water stability as well as resistance to methylation and sulfuration even under forcing conditions. Cyclic voltammetry confirms a high oxidation potential of the compound and computational investigations reveal stabilized orbitals. The unusual orbital stability appears to render the normally electron-rich PI site an extremely poor nucleophile and difficult to oxidize. From a practical perspective, this dye is prepared in a one-pot method under mild conditions. [ABSTRACT FROM AUTHOR]

The uncatalyzed addition of catecholborane to α-diimines has been examined. Reactions proceed smoothly at room temperature in the absence of a catalyst or additive, providing bis-hydroboration products with 3-coordinate boron centres or mono-hydroboration products with 4-coordinate boron centres, depending on the nature of the diimine reagent. [ABSTRACT FROM AUTHOR]

The chemistry of low-coordinate phosphorus-containing species is an area of intense interest in modern main group chemistry. While typical routes for accessing such species include pyrophoric phosphorus-centered precursors or harsh reducing agents, triphosphenium cations represent a more convenient and safer alternative. This Perspective summarizes the use of air- and moisture-stable triphosphenium salts of [dppeP]+ as a source of P+ ions for the generation of a variety of new and/or useful low-coordinate phosphorus-containing species. These range from phosphorus-rich oligomers to phosphamethine cyanine dyes. Special emphasis is placed on the electronic structure of the newly generated species as well as their subsequent reactivity. [ABSTRACT FROM AUTHOR]

The preparation of a series of 4,4′,5,5′-substituted benzo-fused 1,2,5,6-tetrathiocins X2C6H2S4C6H2X2 (1a–1g) were prepared from the reaction of S2Cl2 with 1,2-C6H4X2 (X = OMe, OEt; X2 = OCH2O, OCH2CH2O, OCH2CH2CH2O, MeNC(＝O)NMe, O(CH2CH2O)4). The oxidative addition of 1a–1g to zero-valent Pd2dba3 or Pt2dba3 (dba = dibenzylideneacetone) in the presence of bis (diphenylphosphino)ethane (dppe) resulted in formation of the substituted mononuclear benzenedithiolate complexes M(L)(dppe) [L = dithiolate ligand; 2a–2g (M = Pd) and 3a–3g (M = Pt)] in 37–89% yield based on recrystallized material. Representative examples of M(L)(dppf) [dppf = bis-diphenylphosphinoferrocene; 4a, 4g (M = Pd) and 5g (M = Pt)] were prepared in a similar fashion. The structures of all derivatives were determined by X-ray diffraction, multinuclear NMR and elemental analysis. The reactivity of the two crown ether dithiolate complexes, 2g and 4g, with 1 equivalent of NaBPh4 led to isolation of the 1 : 1 complexes in which the Na+ cation is bound in the macrocyclic crown, [Na(2g)(MeOH)2][BPh4] and [Na(4g)][BPh4] whose structures were determined by X-ray diffraction. Electrochemical studies supported through DFT calculations on the crown ether derivatives revealed a series of ligand-based oxidation waves corresponding to the dithiolate ligand (and dppf for 4g and 5g) whose redox potentials were shifted by ca. +0.1 V on binding to Na+. [ABSTRACT FROM AUTHOR]

Catenation is common for the light main‐group elements whereas it is rare for the heavy elements. Herein, we report the first example of a neutral molecule containing a Bi4 chain. It is prepared in a one‐step reaction between bismuth trichloride and bis(diisopropylphosphino)amine in methanol suspension. The same reaction carried out in dichloromethane gives quite different products. All products have been characterized spectroscopically and using single‐crystal X‐ray analysis. [ABSTRACT FROM AUTHOR]

This investigation examines the reactivity of phosphinoboronate esters Ph2PBpin (pin = 1,2-O2C2Me4) and Ph2PBcat (cat = 1,2-O2C6H4), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR′2 along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the C＝O double bond at elevated temperatures to give the corresponding diphosphines RC(OBR′′2)(PR′2)2. These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh2)2 (2a) with (η5-C9H7)Rh(η2-coe)2 (coe = cis-cyclooctene) affording the indenyl rhodium complex (η5-C9H7)Rh(PhC(OBpin)(PPh2)2) (3a) where the phosphines are bound to the metal centre in a κ2-P,P bidentate manner. [ABSTRACT FROM AUTHOR]

Research has been conducted on 1,2,4-triazol-5-ylidenes. The authors describe the methods developed for the synthesis of these compounds.

The reductive dehalogenation of a zwitterionic GeII species to make a zwitterionic GeI dimer with a 1,2‐dicationic core is reported herein. To the root of the stability of this compound, the molecular and electronic structures were comprehensively characterized and investigated using crystallographic, spectroscopic, and computational methods. It was determined that the Ge centers are attracted because they are both electron‐rich and positively charged. A comparison to the electronic structure in triphosphenium cations revealed varying degrees of covalent bonding and that this difference can be distinguished spectroscopically. [ABSTRACT FROM AUTHOR]

Treatment of MCl2 (M = Ge or Sn) with 2,6-bis(benzimidazol-2-yl)pyridine (G-BZIMPY, G = NBn, N(3,5-CF3)Bn, NAllyl and O) yielded the self-ionization products [G-BZIMPYMCl][MCl3] (1–6) in high yields (75–98%). Reduction reactions are examined and the nickel complexes 8 and 9 ([(NBn-BZIMPY)2Ni][MCl3]2) are isolated from the reaction of Ni(COD)2 with 1 and 2 respectively. [NBn-BZIMPYSnCl][SnCl3] shows a significantly stronger MLCT band in the UV-vis absorption spectrum than its germanium counterparts, with germanium complexes exhibiting negative solvatochromism that is not observed in tin complexes. [ABSTRACT FROM AUTHOR]

Treatment of GaCl3 with 2,6-bis(benzimidazol-2-yl)pyridine (G-BZIMPY, G = NBz, N(3,5-CF3)Bz, N-allyl and O) yielded the autoionization products [G-BZIMPYGaCl2][GaCl4] (1–4) in great yields. The Ga(iii) complex 1 was reduced to Ga(i) using K2[Fe(CO)4], resulting in the complex [(NBzBZIMPY)(Cl)Ga–Fe(CO)4] (7). GaCl3 and AlCl3 were complexed by the structurally similar bis(imino)pyridine (DIMPY) and the resulting complexes are compared to those of G-BZIMPY. [ABSTRACT FROM AUTHOR]

Treatment of two equivalents of the triphosphenium zwitterion L with sources of Ni0 and Pd0 form the mononuclear η2‐diphosphoniodiphosphene complexes 1 and 2. The reaction between L and [FeCp(CO)2]2 results in the binuclear μ‐η1:η1‐diphosphoniodiphosphene iron complex 3, which features an alternative bonding motif of the diphosphoniodiphosphene unit. The formation of these species has been confirmed by spectroscopic methods and single‐crystal X‐ray diffraction analysis, and their electronic structures have been elucidated using computational methods. A diphosphoniodiphosphene is unexpectedly formed by insertion of Ni0, Pd0, and FeI into the P−P bonds of a triphosphenium zwitterion, giving rise to structurally confirmed μ2‐bound monometallic or μ‐η1:η1‐bimetallic species. [ABSTRACT FROM AUTHOR]

A series of complexes with the formulae [(BIMEt3)SnF4−x][OTf]x with x = 1–4 has been synthesized by successive fluoride abstraction from SnF4 with TMSOTf in the presence of the tetradentate nitrogen donor BIMEt3 (tris ((1-ethyl-benzoimidazol-2-yl)methyl)amine). Single crystal X-ray diffraction and heteronuclear NMR spectroscopic analysis provided insight into these new main group cations. Electrospray ionization mass spectrometric analysis on solutions containing the different salts allowed for successful detection of the cations [(BIMEt3)SnF]3+, [(BIMEt3)SnF2]2+ and [(BIMEt3)SnF3]+. [ABSTRACT FROM AUTHOR]

Abstract: A convenient synthesis of dicyanophosphide and dicyanoarsenide anions is reported. These heavy homologues of the long‐known and fundamentally important dicyanamide anion were formed through the nucleophilic displacement of bis(diphenylphosphino)ethane (dppe) from the pnictogen+ transfer agents [dppePn][BPh4] (Pn=P, As) by exposure to cyanide salts. The protocol requires three synthetic steps from commercially available materials and the [dppePn][BPh4] salts are remarkably temperature, air, and moisture stable. All products have been fully characterized by spectroscopic methods and by single‐crystal X‐ray diffraction, and the electronic structures of the DCPn anions have been assessed computationally. [ABSTRACT FROM AUTHOR]

Conformationally flexible cores that generate large free volume when stacked and have an insufficient number of side-chains for filling the lateral space around each core have been proposed as design criteria for discotic liquid crystals that display nematic rather than columnar mesophases. Presented here are 1,3,5-triazines substituted with three thiophene carboxylate ester groups that fulfil these design criteria. Nine derivatives with linear, branched, and chiral ester chains were synthesised and their mesomorphism was studied by polarised optical microscopy, differential scanning calorimetry, and powder x-ray diffraction. Triazines with linear propyl to octyl chains display monotropic nematic discotic mesophases that crystallise within hours or days or when mechanically agitated. Packing structures for the nematic phases are proposed based on the single crystal structure of the ethyl ester. Their unusually slow nucleation and crystal growth can be attributed to the large number of possible low energy conformations that arise from the conformationally flexible core. Incorporation of racemic and chiral branched chains expectedly lowers the melting points of these derivatives but, unexpectedly, enhances nucleation and crystal growth well above the temperature ranges of their hypothetical nematic phases. Chiral nematic discotic mesophases were obtained for binary mixtures of derivatives with chiral branched and linear chains. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of the tris(1-ethyl-benzoimidazol-2-ylmethyl)amine (BIMEt3 = L) complex of Ge(ii)2+ is described. Oxidation of [LGe]2+ with Selectfluor gives [LGeF2]2+, in a process that is envisaged to involve a tricationic complex [LGeF]3+ as an intermediate, which has been isolated by fluoride ion abstraction from [LGeF2]2+. [ABSTRACT FROM AUTHOR]

Abstract: The isolation and full characterisation of a series of cationic metal–carbonyl complexes bearing an N‐heterocyclic carbene stabilised phosphorus(I) ligand are reported. Specifically, the mononuclear coordination complexes [LM(CO)5][BPh4] (M=Cr, Mo, W), [LFe(CO)4][BPh4] and the dinuclear complexes [LMn2(CO)8][BPh4] and [LCo2(CO)6][BPh4], in which L=[bis(1,3,4,5‐tetramethylimidazol‐2‐ylidene)phosphanide]+, have all been isolated in the solid state and structurally confirmed by single‐crystal X‐ray diffraction. The dicationic platinum complex trans‐[L2PtCl2][BPh4]2 is also reported and fully characterised. The donor ability of [L]+ has been assessed by IR spectroscopy of its metal–carbonyl complexes and by using DFT calculations. The results suggest that [L]+ is a weak π‐acceptor with moderate donor strength and thus it bridges the gap that exists between phosphines and amines in terms of ligand properties. Collectively, these molecules represent the first crystallographically characterised cationic metal–carbonyl derivatives of a PI‐centred ligand and are a rare collection of cationic metal–carbonyl complexes. [ABSTRACT FROM AUTHOR]

Abstract: The phosphorus–sulfur heterocycles 1,2‐thiaphosphetenes and phosphirene sulfides have been prepared, and represent the first structurally characterized derivatives for either class of compound. These strained P−S ring systems are formed by the reaction of a phosphinidene sulfide and alkyne. Using an internal alkyne, only the 3‐membered PV, phosphirene sulfide was produced, whereas a terminal alkyne yielded a mixture of phosphirene sulfide and 1,2‐thiaphosphetene (PIII). Detailed computational analysis revealed that for numerous derivatives of alkynes, the corresponding 4‐membered rings are always more stable than the 3‐membered isomers. The electronic nature of “free” phosphinidene sulfides (R−P=S) is discussed based on computational results. [ABSTRACT FROM AUTHOR]

We present the synthesis of a zwitterionic triphosphenium molecule, tBu(C5H2)(PPh2)2PI (L), which can act as a single- or multidentate ligand with group 6, 7, 8 and 9 metal carbonyl complexes. Group 6, [M(CO)5L] complexes are formed under photolytic conditions, where the metal is bound at the P(i) center. In the case of Mo(CO)6, the bimetallic complex [M(CO)5LMo(CO)3] is generated, which features bonds to both the phosphorus(i) center and the cyclopentadienyl moiety of the molecule. Interestingly, group 7 and 9 metal carbonyl dimers generate bimetallic complexes in the form [M2(CO)nL], where both metal centers are bound at the phosphorus(i) center. A detailed analysis of these molecules is provided, including X-ray diffraction, multinuclear NMR, infrared spectroscopy and computational investigations. [ABSTRACT FROM AUTHOR]

The transition metal-free addition of phosphinoboronate ester Ph2PBpin (pin = 1,2-O2C2Me4) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of Ph2PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products. The methodology developed in this study provides a simple and elegant route for the generation of a wide range of functionalized phosphines. The phosphinoboronate ester Ph2PBpin also selectively and reversibly adds to CO2 at room temperature in a 1,2-manner. [ABSTRACT FROM AUTHOR]

The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus(i) reagent [PIdppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine. [ABSTRACT FROM AUTHOR]

The synthesis and characterization of a series of 1,4-dialkyl-1,2,4-triazolium iodide and tetraphenylborate salts featuring methyl, ethyl, and isopropyl substituents and their use as precursors, in conjunction with triphosphenium reagents, to generate 1,4-dialkyl-1,2,4-triazol-5-ylidene-stabilized phosphorus(I) ions is described. The use of tetraphenyl borate salts of both reagents produces the most pure products. The structural and spectroscopic features of the products are compared to those of analogous ions featuring 1,3-imidazol-2-ylidene ligands. [ABSTRACT FROM AUTHOR]

Notable aspects of the chemistry of complexes of polyether ligands including crown ethers, cryptands, glycols, glymes, and related polyether ligands with heavier group 13 and 14 elements are reviewed with a focus on results from 2005 to the present. The majority of reported polyether complexes contain lead(ii) and thallium(i) but recent breakthroughs in regard to the preparation of low oxidation state reagents of the lighter congeners have allowed for the generation of complexes containing indium(i), gallium(i), germanium(ii), and even silicon(ii). The important roles of ligand size, donor types, and counter anions in regard to the chemical properties of the polyether complexes is highlighted. A particular focus on the structural aspects of the numerous coordination complexes provides a rationale for some of the spectacular contributions that such compounds have made to Modern Main Group Chemistry. [ABSTRACT FROM AUTHOR]

The preparation of a novel triphosphenium zwitterion featuring di-, tri-, and tetra-coordinate phosphorus centres derived from a 1,2,4-tris-(diphenylphoshinyl)cyclopentadienyl framework is described. The reactivity of this potentially multidentate donor with protons, elemental sulfur and gold(i) chloride is examined, and the preferential reactivity of the pendant phosphine group over the P(i) centre is rationalized on the basis of density functional theory investigations. [ABSTRACT FROM AUTHOR]

Although salts of thiazolium cations are known, many readily prepared iodide salts have eluded spectroscopic and structural characterization; herein, data for a variety of such salts are reported. It has been demonstrated that thiazolium cations can be deprotonated to generate S,N-heterocyclic carbenes and their “electron rich olefin” dimers, but use of the former has been largely overshadowed by that of the more common N-heterocyclic carbenes. We report herein that the deprotonation of thiazolium iodides and their subsequent reaction with a conveniently prepared triphosphenium precursor grants phosphamethine cyanine cations with solid-state geometry and electronic structure unlike those of NHC-stabilized cations. Protection of the phosphorus atom in such ions with elemental sulfur provides an air- and moisture-stable dithiophosphinium salt. [ABSTRACT FROM AUTHOR]

A convenient one-pot synthesis of chelating bis-N-heterocyclic carbene-ligated PI salts is described. The solid state structures of these remarkably stable phosphamethine cyanine dyes with various N-alkyl groups and counter-anions are reported, and initial reactivity results are discussed. [ABSTRACT FROM AUTHOR]

Two unique systems based on low-coordinate main group elements that activate P4 are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P4, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element-phosphorus bonds and bonding with respect to reforming the P4 tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents. [ABSTRACT FROM AUTHOR]

Attempts to coordinate neutral ligands to low oxidation state indium centers are often hindered by disproportionation pathways that produce elemental indium and higher oxidation state species. In contrast, we find that reactions of the salt, InOTf (OTf=trifluoromethanesulfonate), with α-diimine ligands yielded intensely colored compounds with no evidence of decomposition. X-ray structural analysis of InOTf ⋅MesDABMe (MesDABMe= N, N-dimesityl-2,3-dimethyl-diazabutadiene; 1) reveals a discrete molecular compound with a pyramidal coordination environment at the indium center, consistent with the presence of a stereochemically active lone pair of electrons on indium and a neutral diazabutadiene chelate ligand. The use of the less-electron-rich MesDABH ligand (MesDABH= N, N-dimesityl-diazabutadiene) engenders dramatically different reactivity and produces a metallopolymer (InOTf ⋅MesDABH)∞ ( 2) linked via CC and InIn bonds. The difference in reactivity is rationalized by cyclic voltammetry and DFT studies that suggest more facile electron transfer from InI to the MesDABH and bis(aryl)acenaphthenequinonediimine (BIAN) ligands. Solution EPR spectroscopy indicates the presence of non-interacting ligand-based radicals in solution, whereas solid-state EPR studies reflect the presence of a thermally accessible spin triplet consistent with reversible CC bond cleavage. [ABSTRACT FROM AUTHOR]

A collection of zwitterionic phosphanide metal carbonyl coordination complexes has been synthesized and fully characterized, representing the first isolated series of metal complexes for the triphosphenium family of compounds. The dicoordinate phosphorus atom of the zwitterion is formally in the +1 oxidation state and can coordinate to one metal, 2M (M = Cr, Mo, W) and 2Fe, or two metals, a Co2(CO)6 fragment 4, depending on the starting reagents. All complexes have been isolated in greater than 80% yield, and structures were confirmed crystallographically. Metrical parameters are consistent with 1 being a weak donor and results in long metal-phosphorus bonds being observed in all cases. Unique bimetallic structures, 3M (M = Cr, Mo, W), consisting of a M(CO)5 fragment on phosphorus and a piano-stool M(CO)3 fragment on a boron phenyl group have been identified in the 31P{¹H} NMR spectra and confirmed using X-ray diffraction studies. Use of the borate backbone in 1, which renders the molecule zwitterionic, proves to be a determining factor in whether these metal complexes will form; the halide salt of a cationic triphosphenium ion, 6[Br], shows no evidence for formation of the analogous metal complexes by 31P{¹H} NMR spectroscopy, and tetraphenylborate salts, 6[BPh4] and 7[BPh4], produce complexes that are unstable. [ABSTRACT FROM AUTHOR]

Königs Wasser: Verbindungen mit Germanium(II) ‐ Kronenether ‐ Dikationen reagieren mit Wasser oder Ammoniak zu den stabilen Komplexen [([15]Krone ‐ 5)Ge⋅OH2][OTf]2 (siehe Bild; Ge orange, O rot, F grün, S gelb, H blau) und [([15]Krone ‐ 5)Ge⋅NH3][OTf]2 mit acidifizierten OH ‐ bzw. NH ‐ Wasserstoffatomen. [ABSTRACT FROM AUTHOR]

A series of tin(II) triflate and chloride salts in which the cations are complexed by either cyclic or acyclic polyether ligands and which have well-characterized single-crystal X-ray structures are investigated using a variety of experimental and computational techniques. Mössbauer spectroscopy illustrates that the triflate salts tend to have valence electrons with higher s-character, and solid-state NMR spectroscopy reveals marked differences between superficially similar triflate and chloride salts. Cyclic voltammetry investigations of the triflate salts corroborate the results of the Mössbauer and NMR spectroscopy and reveal substantial steric and electronic effects for the different polyether ligands. MP2 and DFT calculations provide insight into the effects of ligands and substituents on the stability and reactivity of the low-valent metal atom. Overall, the investigations reveal the existence of more substantial binding between tin and chlorine in comparison to the triflate substituent and provide a rationale for the considerably increased reactivity of the chloride salts. [ABSTRACT FROM AUTHOR]

Protonolysis of indium(i) reagents using an [18]crown-6 poly-ether pre-treated with trifluoromethanesulfonic acid (HOTf) provides an efficient route to the known salt [In([18]crown-6)][OTf] in excellent yield. The analogous reaction employing trifluoroacetic acid (HTFA) allows for the isolation of [In([18]crown-6)][TFA], a monovalent indium complex for which the uncrowned salt is not stable at ambient conditions. The direct treatment of indium metal with HOTf, either in the presence or absence of [18]crown-6, provides a high-yield synthetic approach to univalent indium salts that does not require the use of a pre-existing indium(i) reagent. [ABSTRACT FROM AUTHOR]

The treatment of the soluble indium(I) salt [In([18]crown-6)][O_{3}SCF_{3}] with several potassium salts of the form [K][A] results in the release of the indium(I) cation from the crown ether and the production of salts of [K([18]crown-6)]^{+} and uncomplexed [In]^{+}. [ABSTRACT FROM AUTHOR]

Salts containing the decamethylmetallocenium cations, [(C5Me5)2M]+ (or Cp*2M+) of the group 13 “metals” B, Al and Ga have been prepared using a variety of synthetic routes. Precursor molecules of the type Cp*2MX (X = Cl, Br, Me) exhibit structural features that vary significantly depending on the size and electronegativity of the central atom. While salt metathesis, halide abstraction and methanide abstraction methods represent viable routes for the preparation of salts of Cp*2B+ and Cp*2Al+, acidolysis of a Cp* group from Cp*3Ga is the most reliable method for the synthesis of the analogous gallium cation. Gallocenium cations are less stable than either of the lighter congeneric cations since they prove to be susceptible to decomposition reactions involving the “back-transfer” of ligands from the counter anion. Density functional theory (DFT) calculations revealed that, whereas Cp*2Ga+ is predicted to adopt a molecular structure more similar to that of Cp*2B+, the electronic structure of the gallium cation bears a greater resemblance to that of Cp*2Al+. [ABSTRACT FROM AUTHOR]

An improved method for the synthesis of cyclic low oxidation state P cations is presented. The only byproducts of the reaction of phosphorus triiodide with chelating phosphines are readily removed, resulting in an easily accessible PI reagent with an anion that can be readily replaced through salt metathesis chemistry. These P salts are surprisingly stable, even in O2 and moisture, and the origin of this unusual stability is elucidated using density functional theory calculations. [ABSTRACT FROM AUTHOR]