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Phosphorus‐centered disbiradicals, in which the radical sites exist as individual spin doublets with weak spin‐spin interaction have not been known so far. Starting from monoradicals of the type [⋅P(μ‐NTer)2P−R], we have now succeeded in linking two such monoradical phosphorus centers by appropriate choice of a linker. To this end, biradical [⋅P(μ‐NTer)2P⋅] (1) was treated with 1,6‐dibromohexane, affording the brominated species {Br[P(μ‐NTer)]2}2C6H12 (3). Subsequent reduction with KC8 led to the formation of the disbiradical {⋅[P(μ‐NTer)]2}2C6H12 (4) featuring a large distance between the radical phosphorus sites in the solid state and formally the highest biradical character observed in a P‐centered biradical so far, approaching 100 %. EPR spectroscopy revealed a three‐line signal in solution with a considerably larger exchange interaction than would be expected from the molecular structure of the single crystal. Quantum chemical calculations revealed a highly dynamic conformational space; thus, the two radical sites can approach each other with a much smaller distance in solution. Further reduction of 4 resulted in the formation of a potassium salt featuring the first structurally characterized P‐centered distonic radical anion (5−). Moreover, 4 could be used in small molecule activation. [ABSTRACT FROM AUTHOR]

The chemistry of silylated sulfuric acid, O2S(OSiMe3)2 (T2SO4, T=Me3Si; also known as bis(trimethylsilyl) sulfate), has been studied in detail with the aim of synthesizing the formal autosilylation products of silylated sulfuric acid, [T3SO4]+ and [TSO4]−, in analogy to the known protonated species, [H3SO4]+ and [HSO4]−. The synthesis of the [TSO4]− ion only succeeds when a base, such as OPMe3 that forms a weakly coordinating cation upon silylation, is reacted with T2SO4, resulting in the formation of [Me3POT]+[TSO4]−. [T3SO4]+ salts could be isolated starting from T2SO4 in the reaction with [T−H−T]+[B(C6F5)4]− or T+[CHB11Br6H5]− when a weakly coordinating anion is used as counterion. All silylated compounds could be crystallized and structurally characterized. [ABSTRACT FROM AUTHOR]

Conversion of 1,2‐bis(dichlorophosphino)benzene with sterically demanding primary amines led to the formation of 1,3‐dichloro‐2‐aza‐1,3‐diphosphaindanes of the type C6H4(μ‐PCl)2N‐R. Reduction yielded the corresponding 2‐aza‐1,3‐diphosphaindane‐1,3‐diyls (1), which can be described as phosphorus‐centered singlet biradical(oid)s. Their stability depends on the size of the substituent R: While derivatives with R=Dmp (2,6‐dimethylphenyl) or Ter (2,6‐dimesitylphenyl) underwent oligomerization, the derivative with very bulky R=tBuBhp (2,6‐bis(benzhydryl)‐4‐tert‐butylphenyl) was stable with respect to oligomerization in its monomeric form. Oligomerization involved activation of the fused benzene ring by a second equivalent of the monomeric biradical and can be regarded as formal [2+2] (poly)addition reaction. Calculations indicate that the biradical character in 1 is comparable with literature‐known P‐centered biradicals. Ring‐current calculations show aromaticity within the entire ring system of 1. [ABSTRACT FROM AUTHOR]

Tetrahydrocarbazoles and perhydrocyclohepta[b]indoles undergo a catalytic cascade singlet oxygenation in alkaline medium, which leads to chiral tricyclic perhydropyrido‐ and perhydroazepino[1,2‐a]indoles in a single operation. These photooxygenation products are new synthetic equivalents of uncommon C,N‐diacyliminium ions and can be functionalized with the aid of phosphoric acid organocatalysis. [ABSTRACT FROM AUTHOR]

Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN−), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph4P, Ph3PNPPh3=PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2]− and trihydrogen tetracyanide ions [CN(HCN)3]− from liquid HCN when a fast crystallization was carried out at low temperatures. X‐ray structure elucidation revealed hydrogen‐bridged linear [CN(HCN)2]− and Y‐shaped [CN(HCN)3]− molecular ions in the crystal. Both anions can be considered members of highly labile cyanide‐HCN solvates of the type [CN(HCN)n]− (n=1, 2, 3 ...) as well as formal polypseudohalide ions. [ABSTRACT FROM AUTHOR]

The Group 15 open-shell singlet biradicaloid [P(μ-NTer)]2 (Ter=2,6-bis(2,4,6-trimethylphenyl)phenyl) was utilized in the activation of stable small molecules. Fast reactions with H2, CO2, and NH3 were observed. Dihydrogen easily added to [P(μ-NTer)]2 , yielding [HP(μ-NTer)]2 under ambient conditions whereas reversible release of molecular hydrogen was observed at slightly elevated temperatures ( T>60 °C). As [P(μ-NTer)]2 is a species with phosphorus in the unusual formal oxidation state +II, it is capable of reducing carbon dioxide to afford a zwitterionic compound, [OP(μ-NTer)2P], and carbon monoxide. The reaction of [P(μ-NTer)]2 with ammonia led to the formation of an azadiphosphiridine after rearrangements of the central P2N2 heterocycle. [ABSTRACT FROM AUTHOR]

The reaction of [ClP(μ-PMes*)]2 ( 1) with the Lewis acid GaCl3 yielded a hitherto unknown tetraphosphabicyclo[1.1.0]butan-2-ium salt, [Mes*P4(Cl)Mes*][GaCl4] ( 3[GaCl4]), which incorporates a positively charged phosphonium center within its bicyclic P4 scaffold. The formation of the title compound was studied by means of low-temperature NMR experiments. This led to the identification of an intermediate cyclotetraphosphenium cation, which was trapped by reaction with dimethylbutadiene (dmb). All of the compounds were fully characterized by experimental and computational methods. [ABSTRACT FROM AUTHOR]

The systematic study of the reaction of M[PF6] salts and Me3SiCN led to a synthetic method for the synthesis and isolation of a series of salts containing the unprecedented [PF2(CN)4]− ion in good yields. The reaction temperature, pressure, and stoichiometry were optimized. The crystal structures of M[PF2(CN)4] (M=[nBu4N]+, Ag+, K+, Li+, H5O2+) were determined. X-ray crystallography showed the exclusive formation of the cis isomer in accord with 31P and 19F solution NMR spectroscopy data. Starting with the K[PF2(CN)4] the room temperature ionic liquid EMIm[PF2(CN)4] was prepared exhibiting a rather low viscosity. [ABSTRACT FROM AUTHOR]

Main-group singlet biradicaloids have been thoroughly investigated in the past two decades, especially derivatives of cyclobutane-1,3-diyl. However, in each of the known examples, the radical centers are identical. Therefore, we sought to prepare a mixed dipnictadiazanediyls with P and As bearing the radical character. To achieve this goal, the unprecedented cyclodichloro arsaphosphadiazane [ClP(μ-NTer)2AsCl] had to be prepared first. Treatment of [ClP(μ-NTer)2AsCl] with a halide-abstracting agent led to the novel cyclic cation [P(μ-NTer)2AsCl]+, while reduction with magnesium afforded the first arsaphosphadiazanediyl [P(μ-NTer)2As]. [ABSTRACT FROM AUTHOR]

Finally isolated: The isolation of a nitridophosphane(V) was described for the first time by the research group of Bertrand. The reactivity and the possibility of stabilizing labile R2PN/R2NP species (see structure) are discussed. [ABSTRACT FROM AUTHOR]