Darstellung und NMR-spektroskopische Untersuchung eines hexakoordinierten p-Tolylo-tantal(V)-Komplexes: [(p-CH3C6H4)5 Ta(p-CH3C6H4)Li · O(C2H5)2]

Preparation and N.M.R.-spectroscopie Investigation of a Hexacoordinated p-Tolylotantalum(V) Complex: [(p-CH₃C₆H₄)₅Ta(p-CH₃C₆H₄)Li · O(C₂H₅)₂] Reaction of tantalum(V) bromide with an etheral solution of p-tolyllithium in the molar ratio 1:5 leads to precipitation of a yellow complex of the brutto formula LiTaTol₆ · Ae[Tol = p-CH₃C₆H₄^?; Ae = (C₂H₅)₂O]. The ¹H and ¹³C n.m.r. spectra are discussed.     

Synthesis and mesomorphism of mixed ether-ester tail triphenylene discotic liquid crystals with long alkyloxy peripheral chains

Symmetrical and asymmetrical triphenylene discotic liquid crystals with two kinds of different peripheral chains, sym-TP(OC₁₁H₂₃)₃(O₂CR)₃ and asym-TP(OC₁₁H₂₃)₃(O₂CR)₃, (R=CH₂OC₂H₅, CH₂OC₃H₇, CH₂OC₄H₉, CH₂OC₅H₁₁, C₃H₇, C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅) were synthesized. Their thermotropic liquid crystalline properties were studied by polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The results showed that the asymmetrical compounds had higher melting and clearing points than that of their corresponding symmetrical compounds. For the same series of compounds, TP(OC₁₁H₂₃)₃(O₂CR)₃, their melting points decrease and clearing points increase gradually with the lengthening of ester chains. Most of the β-oxygen containing esters of triphenylene derivatives, TP (OC₁₁H₂₃)₃(O₂CR)₃, (R=CH₂OC₂H₅, CH₂OC₃H₇, CH₂OC₄H₉, CH₂OC₅H₁₁), symmetrically or asymmetrically attached on triphenylene cores, have higher melting and clearing points than those of triphenylene derivatives, TP(OC₁₁H₂₃)₃(O₂CR)₃, (R=C₄H₉, C₅H₁₁, C₆H₁₃, C₇H₁₅), with the same length of peripheral chains. The triphenylene derivatives with longer peripheral chains have shown mesophase at room temperature. __________ Translated from Chemical Research and Application, 2007, 19(10) (in Chinese)     

Darstellung und Eigenschaften von π-Cyclopentadienylrhodium-bis(tert.-phosphit)-Komplexen

The half-sandwich type compounds C₅H₅Rh[P(OR)₃]₂ (R = CH₃, C₂H₅, C₆H₅, p-CH₃C₆H₄, p-ClC₆H₄) have been prepared from [(P(OR)₃)₂RhCl]₂ and NaC₅H₅. The NMR. data as well as the IR. and mass spectra of the new compounds will be discussed. The preparation of C₅H₅Rh(CO)P(OC₂H₅)₃ is also reported.     

Organometallic chemistry of chiral diphosphazane ligands: Synthesis and structural characterisation

The diphosphazane ligands of the type, (C₂₀H₁₂O₂)PN(R)P(E)Y₂ (R = CHMe₂ or (S)-*CHMePh; E = lone pair or S; Y₂ = O₂C₂₀H₁₂ or Y = OC₆H₅ or OC₆H₄Me-4 or OC₆H₄OMe-4 or OC₆H₄Bu^t-4 or C₆H₅) bearing axially chiral 1,1'-binaphthyl-2,2′-dioxy moiety have been synthesised. The structure and absolute configuration of a diastereomeric palladium complex, [PdCl₂{ηsu2}-((O₂C₂₀H₁₂)PN((S)-*CHMePh)PPh₂] has been determined by X-ray crystallography. The reactions of [CpRu(PPh₃)₂Cl] with various symmetrical and unsymmetrical diphosphazanes of the type, X₂PN(R)PYY′ (R = CHMe₂ or (S)-*CHMePh; X = C₆H₅ or X₂ = O₂C₂₀H₁₂; Y=Y′= C₆H₅ or Y = C₆H₅, Y′ = OC₆H₄Me-4 or OC₆H₃Me₂-3,5 or N₂C₃HMe₂-3,5) yield several diastereomeric neutral or cationic half-sandwich ruthenium complexes which contain a stereogenic metal center. In one case, the absolute configuration of a trichiral ruthenium complex, viz. [Cp*Ruη₂-Ph₂PN((S)-*CHMePh)*PPh (N₂C₃HMe₂-3,5)Cl] is established by X-ray diffraction. The reactions of Ru₃(CO)₁₂ with the diphosphazanes (C₂₀H₁₂O₂)PN(R)PY₂ (R = CHMe₂orMe; Y₂=O₂C₂₀H₁₂or Y= OC₆H₅ or OC₆H₄Me-4 or OC₆H₄OMe-4 or OC₆H₄Bu^t-4 or C₆H₅) yield the triruthenium clusters [Ru₃(CO)₁₀{η-(O₂C₂₀H₁₂)PN(R)PY₂}], in which the diphosphazane ligand bridges two metal centres. Palladium allyl chemistry of some of these chiral ligands has been investigated. The structures of isomeric η³-allyl palladium complexes, [Pd(η³-l,3-R′₂-C₃H₃){η²-(rac)-(0₂C₂₀H₁₂)PN(CHMe₂)PY₂}](PF₆) (R′ = Me or Ph; Y = C₆H₅ or OC₆H₅) have been elucidated by high field two-dimensional NMR spectroscopic and X-ray crystallographic studies.     

Complexation of the 2, 4, 6‐Triallyloxy‐1, 3, 5‐triazine with Copper(I,II) Chlorides. Syntheses and Crystal Structures of [CuCl2·2C3N3(OC3H5)3], [Cu7Cl8·2C3N3(OC3H5)3], and [Cu8Cl8·2C3N3(OC3H5)3]·2C2H5OH

Interaction of copper(II) chloride with 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine leads to formation of copper(II) complex [CuCl₂·2C₃N₃(OC₃H₅)₃] ( I ). Electrochemical reduction of I produces the mixed‐valence Cu^{I, II} π, σ‐complex of [Cu₇Cl₈·2C₃N₃(OC₃H₅)₃] ( II ). Final reduction produces [Cu₈Cl₈·2C₃N₃(OC₃H₅)₃]·2C₂H₅OH copper(I) π‐complex ( III ). Low‐temperature X‐ray structure investigation of all three compounds has been performed: I : space group P1¯, a = 8.9565(6), b = 9.0114(6), c = 9.7291(7) Å, α = 64.873(7), β = 80.661(6), γ = 89.131(6)°, V = 700.2(2) ų, Z = 1, R = 0.0302 for 2893 reflections. II : space group P1¯, a = 11.698(2), b = 11.162(1), c = 8.106(1) Å, α = 93.635(9), β = 84.24(1), γ = 89.395(8)°, V = 962.0(5) ų, Z = 1, R = 0.0465 for 6111 reflections. III : space group P1¯, a = 8.7853(9), b = 10.3602(9), c = 12.851(1) Å, α = 99.351(8), β = 105.516(9), γ = 89.395(8), V = 1111.4(4) ų, Z = 1, R = 0.0454 for 4470 reflections. Structure of I contains isolated [CuCl₂·2C₃N₃(OC₃H₅)₃] units. The isolated fragment of I fulfils in the structure of II bridging function connecting two hexagonal prismatic‐like cores Cu₆Cl₆, whereas isolated Cu₆Cl₆(CuCl)₂ prismatic derivative appears in III . Coordination behaviour of the 2, 4, 6‐triallyloxy‐1, 3, 5‐triazine moiety is different in all the compounds. In I ligand moiety binds to the only copper(II) atom through the nitrogen atom of the triazine ring. In II ligand is coordinated to the Cu^II‐atom through the N atom and to two Cu^I ones through the two allylic groups. In III all allylic groups and nitrogen atom are coordinated by four metal centers. The presence of three allyl arms promotes an acting in II and III structures the bridging function of the ligand moiety. On the other hand, space separation of allyl groups enables a formation of large complicated inorganic clusters.     

Polarographic behaviour of π-allylic complexes of transition metals : II. π-allyltricarbonylcobalt and some phosphinic derivatives

The polarographic reduction in acetonitrile (ACN) of π-C₃H₅Co(CO)₃ and of the phosphinic derivatives π-C₃H₅Co(CO)₂L [L = P(OC₆H₅)₃, P(OCH₂)₃CC₂H₅, P(C₆H₅)₃, P(OC₂H₅)₃, P-n-Bu₃, P(C₆H₁₁)₃] is reported and the reduction mechanism is discussed. The dependence of the E_{$\text{1}\text{2}$} of thecomplexes on the properties of the ligands is analysed, and a linear plot of E_{$\text{1}\text{2}$} vs. ΔHNP of the ligands is observed. The pseudo first-order rate constants for the reduction of the complexes with NaBH₄ in ACN are reported.     

Formation of 1,4- and 1,5-regioisomers of triazolines in reactions of 2-ethoxyethyl azide with monosubstituted ethylenes

The structural specificity of the reactions of 2-ethoxyethyl azide with alkenes RCH=CH₂ [R=CH₂C₆H₅, CH₂OC₆H₁₃, CH(OC₂H₅)₂, C₆H₅] was studied. The formation of 1,4- and 1,5-substituted triazolines and the high stabilities of the latter were demonstrated by PMR spectroscopy, data from gas-liquid chromatography (GLC), and the kinetics of thermolysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–803, June, 1987.     

Kinetische untersuchungen an carbonyl(diorganyldithiophosphinato)-komplexen des mangans und rheniums

The substitution reactions of monomeric dithiophosphinato complexes R₂ PS₂ M(CO)₄ (R = C₂ H₅, C₆H₅; M = Mn, Re) with monodentate ligands P(C₆H₅)₃, As(C₆H₅)₃ and pyridine are examined kinetically. The reactions with P(C₆H₅)₃ and pyridine follow first-order and those with As(C₆H₅)₃ second-order kinetics. The rate constants as well as activation parameters are calculated and discussed in detail together with the reaction mechanism.     

Synthesis and reactivity of some isocyanide complexes of iridium(I)

Several isocyanide complexes [Ir(RNC)₄]X (I) (R = p-CH₃C₆H₄, X = I; R = p-CH₃OC₆H₄, X = I and PF₆) and [Ir(RNC)₂(PPh₃)₃] ClO₄(II) (R = p-CH₃C₆H₄ and p-CH₃OC₆H₄) have been prepared by the reactions of [Ir(COD)Cl]₂ and [Ir(COD)(PPh₃)₂]ClO₄ (COD = l,5-cyclooctadiene) with aryIisocyanides, respectively. Oxidative addition reactions of I and II with halogens, and II with π-acids such as tetracyanoethylene(TCNE), fumaronitrile, maleic anhydride, dimethyl fumarate, acrylonitrile, and dimethyl acetylenedicarboxylate are described. The structures of I, II and the π-acid addition products of II, [Ir(p-CH₃C₆H₄NC)₂ (PPh₃)₂ (π-acid)]ClO₄ (IV) (π-acid = TCNE, fumaronitrile, maleic anhydride, and acetylene dicarboxylate), are discussed on the basis of their electronic, IR, and NMR spectra. Especially, I is suggested to have an unusual layer structure involving Ir to Ir interaction, the result of which is relatively low reactivity in oxidative addition reactions. Trigonal bipyramidal configurations are suggested for IV with the two isocyanides in the trans and cis positions for the olefin and acetylene adducts, respectively.     

Darstellung und eigenschaften von und reaktionen mit metallhaltigen heterocyclen: XXXIII. Synthese und kristallstruktur von (μ3-thio)(μ3-organophosphido)tris(tricarbonyleisen)-(2Fe-Fe)-komplexen

The cluster compounds (μ₃-S)(μ₃-PR)Fe₃(CO)₉ are obtained by reaction of the dichloroorganylphosphane sulphides RP(S)Cl₂ (R = CH₃, 4-CH₃OC₆H₄, C₆H₅) with Na₂[Fe(CO)₄] in ether under cleavage of the PS bond. On the basis of X-ray crystallographic determinations the iron clusters crystallize for R = 4-CH₃OC₆H₄ and C₆H₅ in the monoclinic and triclinic space group C2/c and P$\text{1}$ with Z = 8 and 4, respectively.     

Hypercoordinated compounds of gold(I)

Mono- and binuclear gold(I) derivatives ofortho-substituted diphenyl ether, C₆H₅OC₆H₄AuPPh₃ and O(C₆H₄)₂(AuPPh₃)₂, were prepared by the reaction of the 2,2'-dilithium derivative of diphenyl ether with ClAuPPh₃. X-Ray structural study has shown that these compounds contain secondary intramolecular bonds between the gold and oxygen atoms. The interaction of C₆H₅OC₆H₄AuPPh₃ with (AuPPh₃)BF₄ affords the [C₆H₅OC₆H₄(AuPPh₃)₂]BF₄ cationic complex. The latter reacts with PPh₃ to give the starting C₆H₅OC₆H₄AuPPh₃ complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 729–736, April, 1994.The authors wish to thank A. L. Blyumenfel'd for recording³¹P NMR spectra, D. V. Zagorevskii and K. V. Kazakov who obtained mass spectra, and Yu.L. Slovokhotov who carried out the EXSAFS study.The study described in the present paper was partly supported by the International Scientific Fund, grant N Ch. 002479.     

Some ring replacement and nucleophilic substitution reactions of η6-subsituted arene-η5-cylopentadienyliron hexafluorophosphates

A number of nitroarene and aminoarene complexes, including the PF₆^? salts of NO₂C₆H₅FeCp^p+, 0-, m- or p-CH₃(NO₂)C₆H₄FeCp⁺, NH₂C₆H₅FeCp^p+ and 0-, m-, orp-CH₃(NH₂)C₆H₄FeCp^p+, when heated with an excess of P(OC₂H₅)₃ all gave rise to the ring replacement product, CpFe(P(OC₂H₅)₃)₃⁺ PF₆^? (I). Similarly, the thermal reaction of NO₂C₆H₅Fe(CH₃)Cp⁺ PF₆^? or NH₂C₆H₅Fe(CH₃)Cp⁺ PF₆^? with P(OC₂H₅)₃ gave CH₃CpFe(P(OC₂H₅)₃)₃⁺ PF₆^? (VII). With m-CH₃(Cl)C₆H₄-FeCp⁺ PF₆^? (XIV), heating with P(OC₂H₅)₃ also gave rise to I, while the same treatment with P(OC₂H₅)₃ at room temperature in CH₂Cl₂ showed no nucleophilic substitution of the chlorine atom of XIV by P(OC₂H₅)₃. On the other hand, the chlorine atom of a number of chloroarene complexes could be readily displaced at room temperature with various amines acting as nucleophiles. Such nucleophilic substitutions were carried out on ClC₆H₅FeCp⁺ PF₆^? and 0-, m- or p-CH₃(CI)C₆H₄FeCp⁺ PF₆^? with methylamine, ethylenediamine, cyclohexylamine, benzylamine and pyrrolidine to give rise to 20N-substituted aminoarene complexes.     

MASSENSPEKTROMETRISCHE UNTERSUCHUNGEN AN ORGANOPHOSPHORVERBINDUNGEN I Zum Massenspektrometrischen Fragmentierungsverhalten von Dithio- und Thiophosphonsäureanhydriden

Abstract

70 eV electron impact mass spectra of dimeric dithiophosphonic acid anhydrides [RP(S)S]₂ (R = CH₃, C₆H₅, p-CH₃OC₆H₄, p-C₂H₅OC₆H₄, 2-Thienyl, 2-Naphthyl) and trimeric thiophosphonic acid anhydrides [RP(S)O]₃ (R = CH₃, C₆H₅, Cyclohexyl) are reported and discussed. General fragmentation patterns which are consistent with DADI metastable spectra are suggested for both classes of compounds. Molecular ions are observed in all cases. While in the earlier class ring fission followed by migration of R from phosphorus to sulphur is dominating, the –P–O–P– ring in the latter seems to be rather stable.

Elektronenstoß induzierte 70 eV Massenspektren der dimeren Dithiophosphonsäureanhydride [RP(S)S]₂ (R = CH₃, C₆H₅, p-CH₃OC₆H₄, p-C₂H₅OC₆H₄, 2-Thienyl, 2-Naphthyl) und trimeren Thiophosphonsäureanhydride [RP(S)O]₃ (R = CH₃, C₆H₅, Cyclohexyl) werden aufgeführt und diskutiert. Allgemeine Fragmentierungsschemata, die durch Metastabilenspektren nach der Methode DADI erhärtet worden sind, werden für beide Verbindungsklassen vorgeschlagen. Molekülionen werden in allen Fällen beobachtet. Während für die erste Verbindungsklasse Ringspaltung, gefolgt von einer Wanderung des Substituenten R vom Phosphor zum Schwefel, der dominierende Zerfallschritt ist, besitzt der –P–O–P– Ring der zweiten Verbindungsklasse eine ziemliche Stabilität.     

有玻璃态和液晶态的胆甾烯基苯并菲的合成及介晶性

将盘状液晶基元苯并菲与手性向列型液晶基元胆甾烯基结合的化合物, 可望出现全新的性质. 合成了含有胆甾烯基的苯并菲化合物C₁₈H₆(OC₅H₁₁)₅(OC₅H₁₀COOCh) (2), 2,7-C₁₈H₆(OC₅H₁₁)₄(OC₅H₁₀COOCh)₂ (4), C₁₈H₆(OR)₃(OC_nH_{2nCOO- Ch)3 (R＝C5H11, C7H15, C9H19, C11H23, n＝1, 5, 10) (6a～6f), C18H6(OC5H10COOCh)6 (Ch: cholesteryl) (8). 偏光显微镜和差示扫描量热法对这些化合物的热致介晶性研究结果显示, 化合物 4, 6a～6e具有手性盘状向列相和玻璃态, 8呈现近晶B相(SB)和玻璃态. 随间隔基长度n和烷基链R碳原子数的增加, 化合物玻璃化温度和清亮点呈下降趋势. 随着胆甾烯基数目减少, 化合物的玻璃化温度和清亮点降低.}     

Mechanism of reductive elimination of benzonitrile in cyanophenyl complexes of nickel(II) : II. Reactions of [cyano(phenyl)bis(tricyclohexylphosphine)nickel(II)]

The thermal decomposition of the complex Ni(CN)(C₆H₅)(PCy₃)₂ (Cy = cyclohexyl) in decalin has been examined. The complex reacts with P(OC₂H₅)₃ to give C₆H₅CN in quantitative yield. The mechanism of this reaction has been investigated and compared with that of the similar reaction shown by Ni(CN)(C₆H₅)(PEt₃)₂. The results indicate that the easiest path for the reaction involves a bimolecular attack of P(OC₂H₅)₃ at the metal atom before reductive elimination of C₆H₅CN.     

Cupro(I)-π-complexes with 1-allyloxybenzotriazole: Synthesis and crystal structure of CuBF4 · 2C6H4N3(OC3H5) · H2O and CuCF3COO · C6H4N3(OC3H5)

The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) Å, β = 98.13(1)°, V = 2249(2) ų, Z = 4, R = 0.0705, 577 reflections; I, space group P $ P\bar 1 The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) ?, β = 98.13(1)°, V = 2249(2) ?³, Z = 4, R = 0.0705, 577 reflections; I, space group P , a = 8.8625(7), b = 9.0647(4), c = 9.1650(5) ?, α = 68.37(2)°, β = 85.31(3)°, γ = 69.86(2)°, V = 646(4) ?³, Z = 2, R = 0.1354, 2669 reflections. In compound I, the tetrahedrally distorted trigonal pyramidal environment of the copper atom comprises two nitrogen atoms of two organic molecules (L), the C=C bond of another L molecule, and the O atom of the water molecule. Due to the bridging function of L molecule, infinite chains [Cu · 2C₆H₄N₃(OC₃H₅) · H₂O] _n are formed in the structure along the y axis. The chains are, in turn, assembled into layers through strong O-H…F hydrogen bonds involving both hydrogen atoms of the water molecule and fluorine atoms of the BF₄⁻ anion. In compound II, two bridging oxygen atoms of two trifluoroacetate anions and two copper atoms form a centrosymmetric dimer. The nitrogen atom of the benzotriazole ring of one molecule L and the C=C double bond of the allyl group of the other molecule L complete the distorted coordination tetrahedron of the metal atom. Owing to the bridging function of the L molecule, the [CuCF₃COO · C₆H₄N₃(OC₃H₅)]₂ dimers are connected to form infinite double chains associated in a three-dimensional framework by only weak interactions. The replacement of the covalently bonded trifluoroacetate anion by an outer-sphere tetrafluoroborate ion opens up the possibility for metal atom binding to three L molecules simultaneously. Original Russian Text ? E.A. Goreshnik, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 826–830.     

Aroyl anion trapping reactions. A preliminary study of direct nucleophilic aroylation by means of low temperature, insitu (CH3)nC6H5nLi/CO Systems.

Results of studies of the $\text{in}$$\text{situ}$ nucleophilic aroylation of PhCO₂Me, Me₃CCO₂Me and Ph₂CO by several low temperature ArLi/CO systems (Ar =C₆H₅, p-CH₃C₆H₄, $\text{o}$-CH₃C₆H₄, 2,6-(CH₃)₂C₆H₃ and 2,4,6-(CH₃)₃C₆H₂) are reported. The experiments with C₆H₅Li were unsuccessful and the best results were obtained with 2,6-(CH₃)₂-C₆H₃Li.     

Synthesis and Characterization of 1,3,2‐Bis (arylamino) phospholidine, 2‐oxide Derivatives: Crystal Structures of $\rm Cl(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$ and $\rm ((CH_{2}C_{6}H_{5})(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$

Using phosphoryl chloride as a substrate, a family of 1,3,2‐bis(arylamino) phospholidine, 2‐oxide of the general formula ; (X=Cl, 6a ; X=NMe₂, 1b ; X=N(CH₂C₆H₅)(CH₃), 2b ; X=NHC(O)C₆H₅, 3b ; X=4Me‐C₆H₄O, 4b ; X=C₆H₅O, 5b ; X=NHC₆H₁₁, 6b ; X=OC₄H₈N, 7b ; X=C₅H₁₀N, 8b ; X=NH₂, 9b ; X=F, 10b and Ar=4Me‐C₆H₄) was prepared and characterized by ¹H, ¹⁹F, ³¹P and ¹³C NMR and IR spectroscopy, and elemental analysis. A general and practical method for the synthesis of these compounds was selected. The structures of 6a and 2b were determined by single‐crystal X‐ray diffraction techniques. The low temperature NMR spectra of 2b revealed the restricted rotation of P‐N bond according to two independent molecules in crystalline lattice.     

Interaction of 1,3,2,4‐Benzodithiadiazines with Aromatic Phosphines and Phosphites

Although an interaction between hydrocarbon and fluorocarbon 1,3,2,4‐benzodithiadiazines ( 1 ) and P(C₆H₅)₃ continuously produces chiral 1,2,3‐benzodithiadiazol‐2‐yl iminophosporanes ( 2 ; in this work, 5,7‐difluoro derivative 2a ) via 1:1 condensation, an interaction between 1 and other PR₃ reagents gives different products. With R  OC₆H₅ and both hydrocarbon and fluorocarbon 1 , only X=P(OC₆H₅)₃ (X = S, O) were identified in the complex reaction mixtures by ¹³С and ³¹Р NMR and GC‐MS. With R = C₆F₅, no interaction with the archetypal 1 was observed but catalytic addition of atmospheric water to the heterocycle afforded 2‐amino‐N‐sulfinylbenzenesulfenamide ( 4 ). With electrophilic B(C₆F₅)₃ instead of nucleophilic P(C₆F₅)₃, only adduct H₃N→B(C₆F₅)₃ and a new polymorph of C₆F₅B(OH)₂ were isolated and identified by X‐ray diffraction (XRD). A molecular structure of 2a was confirmed by XRD, and the π‐stacked orientation of one of phenyl groups and heterocyclic moiety was observed. This structure is in general agreement with that calculated at the RI‐MP2 level of theory, as well as at three different levels of DFT theory with the PBE and B3LYP functionals. Mild thermolysis of 2a in a dilute decane solution gave persistent 5,7‐difluoro‐1,2,3‐benzodithiazolyl ( 3a ) identified by EPR in combination with DFT calculations.