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A new benzimidazolyl terpyridyl ligand (BIT) selectively detects Fe2+, F- and CN- ions in acetonitrile. The Fe2+ complex [Fe(H-BIT)2]·(ClO4)4 (1) displays the fast and selective detection of 2,4,6-trinitrophenol (TNP) with strong binding (log β = 8.51 ± 0.24) and a low limit of detection (1.4 × 10-7 M) among several nitroaromatics. The color of complex 1 changes from purple to red, yellow, and green upon the separate addition of 2,4,6-trinitrophenol and tetrabutylammonium salts of fluoride and cyanide, respectively. The overall color changes thus display a model of a traffic light. The structures of BIT, 1 and [Fe(BIT)2]·(TNP)2 (2) have been well characterized using spectroscopic techniques and single crystal X-ray crystallography.

This article reports the reduction of the chloride [PhC(NtBu)2]GeCl with potassium in THF to afford the reddish crystals of [PhC(NtBu)2]2Ge2 (2). The molecule of 2 contains a Ge−Ge bond. The X-ray structure and DFT calculation indicate that the Ge−Ge bond possesses an unusual gauche-bent geometry. The Ge−Ge bond length in 2 is 2.570 A, which is very close to the single Ge−Ge interaction (2.61 A) but significantly longer than that for typical digermenes, R2GeGeR2 (2.21−2.51 A) and the two structurally characterized digermynes (2.2850 A and 2.2060 A), which proves that there is no multiple bond character in 2.

Reduction of LAlI(2) (1) (L = HC[(CMe)(NAr)](2), Ar = 2,6-i-Pr(2)C(6)H(3)) with potassium in the presence of alkynes C(2)(SiMe(3))(2), C(2)Ph(2), and C(2)Ph(SiMe(3)) yielded the first neutral cyclopropene analogues of aluminum LAl[eta(2)-C(2)(SiMe(3))(2)] (3), LAl(eta(2)-C(2)Ph(2)) (4), and LAl[eta(2)-C(2)Ph(SiMe(3))] (5), respectively, whereas reduction of 1 in the presence of Ph(2)CO gave an aluminum pinacolate LAl[O(2)(CPh(2))(2)] (6), irrespective of the amount of Ph(2)CO employed. The unsaturated molecules CO(2), Ph(2)CO, and PhCN inserted into one of the Al-C bonds of 3 leading to ring enlargement to give novel aluminum five-membered heterocyclic systems LAl[OC(O)C(2)(SiMe(3))(2)] (7), LAl[OC(Ph)(2)C(2)(SiMe(3))(2)] (8), and LAl[NC(Ph)C(2)(SiMe(3))(2)] (9) in high yields. In contrast, 3 reacted with t-BuCN, 2,6-Trip(2)C(6)H(3)N(3) (Trip = 2,4,6-i-Pr(3)C(6)H(2)), and Ph(3)SiN(3) resulting in the displacement of the alkyne moiety to afford LAl[N(2)(Ct-Bu)(2)] (10) with an unprecedented aluminum-containing imidazole ring, and the first monomeric aluminum imides LAlNC(6)H(3)-2,6-Trip(2) (11) and LAlNSiPh(3) (12). All compounds have been characterized spectroscopically. The variable-temperature (1)H NMR studies of 3 and ESR measurements of 3 and 4 suggest that the Al-C-C three-membered-ring systems can be best described as metallacyclopropenes. The (27)Al NMR resonances of 2 and 3 are reported and compared. Molecular structures of compounds 3, 4, 6.OEt(2), 8.OEt(2), and 9 were determined by single-crystal X-ray structural analysis.

The first phosphonate anions of aluminum-containing fluorine and an anionic bridged fluoroalkoxy derivative of titanium have been realized using n-Bu4NHF2 as a fluorinating agent in organometallic synthesis. Reactions of [RPO3AlMe]4 [R = Ph (1), t-Bu] with n-Bu4NHF2 yield organic-soluble compounds of the type [n-Bu4N]2[RPO3AlF2]2 [R = Ph (2), t-Bu (3)], whereas the reaction of Ti(O-i-Pr)4 with n-Bu4NHF2 results in the formation of [n-Bu4N][O-i-Pr)3Ti(mu-F)2(mu-O-i-Pr)Ti(O-i-Pr)3] (4). These compounds have been obtained in high yields and have been adequately characterized through spectroscopic techniques and X-ray diffraction studies.

Die Fluorierung von FSO2NH2 bei Raumtemperatur fuhrt in kurzer Zeit in hoher Ausbeute zu FSO2NF2. Die Umsetzung von FSO2NF2 mit Et2NH liefert FSO2NEt2 und HNF2. Der molekulare Aufbau von FSO2NF2 wurde durch Elektronenbeugung bestimmt. Das Molekul besitzt Cs-Symmetrie. Auffallend ist der relativ lange SN-Abstand von 175,5(6) pm. Preparation, Structure, and Reactions of N,N-Difluorosulfonylfluoridamide FSO2NF2 is obtained in high yield by fluorination of FSO2NH2 at room temperature. The reaction of FSO2NF2 with Et2NH yields FSO2NEt2 and HNF2. The structure of FSO2NF2 was determined by electron diffraction analysis.

Durch eine Austauschreaktion werden aus C6H5SO2NSO und CH3SO2NSO mit Tris(trimethylstannyl)amin die substituierten Amide, C6H5SO2N[Sn(CH3)3]21 und CH3SO2N · [Sn(CH3)3]22 erhalten. Beim Erhitzen geht CH3SO2N[Sn(CH3)3]2 in das Tristannazan [CH3SO2NSn(CH3)2]33 uber. Mit (CH3)3SiCl reagiert 3 zum gemischtsubstituierten Amid, CH3SO2NSn(CH3)2ClSi(CH3)34. Die Zusammensetzung der Verbindungen konnte anhand von Massen -, IR - und NMR - Spektren bestatigt werden. Synthesis and Reactions of Bis(trimethylstannyl)sulfonylamides By an exchange reaction C6H5SO2N[Sn(CH3)3]21 and CH3SO2N[Sn(CH3)3]22 were obtained, using C6H5SO2NSO as well as CH3SO2NSO and tris(trimethylstannyl)amine as starting materials. On heating CH3SO2N[Sn(CH3)3]2 the tristannazane [CH3SO2NSn(CH3)2]33 is formed. 3 reacts with (CH3)3SiCl to yield the mixed substitued amide,CH3SO2NSn(CH3)2ClSi(CH3)34. On the basis of mass, i.r. and n. m. r. spectra the compounds were characterized.

Die Reaktion von ClSCF2CF2SCl 1 mit (CH3)3CC(O)CH3, Hexen, Diacetyl, Cyclobutanon und H2CCHC(O)CH3 fuhrt zu den cyclischen und acyclischen Substitutionsprodukten 2–6. Es sind destillierbare Flussigkeiten, die anhand von Elementaranalysen, Massenspektren, 19F-, 13C- und 1H-NMR-Spektren charakterisiert wurden. Der Reaktionsmechanismus wird diskutiert. Reactions of Tetrafluoro-1, 2-ethanedisulfenyldichloride with Ketones and Olefines The reaction of ClSCF2CF2SCl 1 with (CH3)3CC(O)CH3, hexene, diacetyl, cyclobutanone, and H2CCHC(O)CH3 leads to the cyclic and acyclic products 2–6. They are destillable liquids, which have been characterized on the basis of elemental analysis, mass spectra, 19F-, 13C-, and 1H-n.m.r. spectra. The reaction mechanism will be discussed.

The reaction of N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea with PCl3 leads to the bicyclic compound OP2[MeNCONMe]2 (3) with a direct phosphorus-phosphorus bond and to the bicycle MeNP2[MeNCONMe]2 (4). 3 reacts with tetrachloro-o-benzoquinone (TOB) to yield the spirocycle Ce6Cl4tMeNCONMe]2P2O (5) with a λ4P-λ5P-bond. The Lewis acids SbCl5 and SnCL4 react with 3 to give the adducts 6 and 7. The reactions of 3 with the metal carbonyls Fe2(CO)9, Cr(CO)5THF and Cr(CO)4C7H8 lead to the metal complexes 8-10. The compounds were characterized on the basis of 31P NMR and mass spectra.

Das dunkelblauviolette Cyclotrithiatriazendioxid-Anion S3N3O2− konnte auf verschiedenen Wegen dargestellt werden: 1. Umsetzung von S4N4O2 mit Alkaliaziden, 2. Reaktion von (CH3)3ES3N3O2 (E = Si, Sn) mit CsF, 3. Addition von S4N4O2 und Alkali-bis(trimethylsilyl)-amiden mit anschliesendem Kationenaustausch mit Tetraphenylarsoniumchlorid und 4. Umsetzung von S4N4O2 mit Trimethylsilyliminotriphenylphosphoran im Molverhaltnis von 1:1. Ein uberschus des Iminophosphorans fuhrt zur Bildung eines kovalenten 1,5-disubstituierten S4N4-Derivats. Reaktionsmechanismen werden diskutiert und Strukturvergleiche an Trithiatriazinanionen durchgefuhrt. Syntheses of the Anion S3N3O2−, a Stable Six-membered Sulfur-Nitrogen Ring with an 8π-Electron Skeleton The dark blue-violet cyclotrithiazene-dioxide anion S3N3O2−has been synthesized on different pathways: 1. reaction of S4N4O2 with alkali azides, 2. metathesis of (CH3)3ES3N3O2 (E = Si, Sn) with CsF, 3. addition of S4N4O2 and alkali bis(trimethylsilyl)-amides followed by cation exchange with tetraphenylarsonium chloride, and 4. reaction of S4N4O2 with trimethylsilyliminotriphenylphosphorane in a molar ratio of 1:1. Excess iminophosphorane leads to the formation of a covalent 1.5-disubstituted S4N4 derivative. Reaction mechanisms will be discussed and structures of trithiatriazine-anions will be compared.

R-P(Se)F2- (R = CH3, C2H5, C3H11, C6H5, N(CH3)2, N(C2H5)2, NHSi(CH3)3) and R-P(Se)FCl-compounds (R = CH3, C2H5) can be prepared by reaction of R-P(Se)Cl2-derivatives with antimony(III)fluoride under reduced pressure. In some cases the oxidation of fluorophophines with elemental selenium is successful. The isolated compounds are colourless volatile liquids which are sensitive to air and moisture. The chemical properties are described. 1H-, 19F-, 31P-NMR-, IR- and Raman-spectroscopic data are given. Main stretching frequencies are discussed by comparison with similar oxygen- and sulphur-compounds.

P4S10 (1) kann mit Silicium–Stickstoffverbindungen abgebaut werden. 1 reagiert mit (CH3)3Si–N(CH3)2 (2a) bzw. (CH3)3Si–N(C2H5)2 (2 b) zu S = P[N(CH3)2]2SSi(CH3)3 (3a) bzw. 3b. Die Umsetzung von 1 mit [(CH3)3Si]2S (4) ergibt in hoher Ausbeute SP[SSi(CH3)3]3 (6). Um den Reaktionsverlauf aufklaren zu konnen, wurde (C6H5PS2)2 (7) als Modellsubstanz mit 2a bzw. 4 umgesetzt, wobei C6H5P(S)[N(CH3)2]SSi(CH3)3 (9) bzw. C6H5P(S)[SSi(CH3)3]2 (10) entstehen, Der Reaktionsmechanismus wird diskutiert. Die Kernresonanzdaten und Massenspektren werden mitgeteilt. Reactions of P4S10 with Organosilicon Compounds P4S10 (1) can be degraded with silicon-nitrogen compounds. 1 reacts with (CH3)3SiN(CH3)2 (2 a) and (CH3)3SiN(C2H5)2 (2 b) to yield SP[N(CH3)2]2SSi(CH3)3 (3 a) and (3 b). By the reaction of 1 with [(CH3)3Si]2S (4) SP[SSi(CH3)3]3 (6) is formed in high yield. (C6H5PS2)2 (7) was used as a model to investigate the course of the reaction. This leads to C6H5P(S)[N(CH3)2]SSi(CH3)3 (9) and C6H5P(S)[SSi(CH3)3]2 (10). The reaction mechanism will be discussed. The n.m.r. data and mass spectra are reported.

Es werden die Schwingungsspektren von OSPF, S2PF, S2PF(CH3)− und S2P(CN) vermessen und gemeinsam mit O2PF und S2P(CH3) diskutiert und zugeordnet. Anhand der nach einem Naherungsverfahren berechneten Kraftkonstanten werden die Bindungsverhaltnisse besprochen. Die negative Ionenladung bewirkt eine starke Erniedrigung von f PF. Die Ionenladung ist annahernd uber alle beteiligten Atome verteilt. Vibration spectra and force constants of the series O2PF — S2PF — S2P(CH3). The vibrational spectra of OSPF, S2PF, S2PF(CH3) and S2P(CN) are reported and discussed with O2PF and S2P(CH3). On the basis of a simplified valence-force-field the force constants are calculated and the bonding relations are discussed. In the ions, f PF is lower than in corresponding molecules. The ionic charge is distributed over nearly all atoms of the ions.

Die IR-Spektren von flussigen Phosphor-fluorid-isothiocyanaten werden im Bereich zwischen 4000 und 420 cm−1 gemessen und teilweise zugeordnet. Der Gang der charakteristischen Valenzschwingungen wird in homologen Reihen diskutiert. Aus der Lage der PO-Valenzschwingungen ergibt sich, das die formale Elektronegativitat der — NCS-Gruppe zwischen derjenigen von Chlor und Brom liegt. The infrared spectra of phosphorus fluoride isothiocyanates are reported and discussed.

Phenyltetrafluorphosphoran reagiert in Gegenwart von Triäthylamin mit S=PF2NH2 oder S=PFClNH2, S = PCl2NH2, FSO2NH2, P3N3F5NH2 zu den neuen Verbindungen S=PF2N = PF2CeH5, S = PFClN =PF2C6H5, S = PCl2N = PF2C6H5, FSO2N = PF2C6H5 und P3N3F5N= PF2CeH5. Die Verbindungen werden durch ihre Elementaranalyse, IR-Spektren und 19F-, 31P- und 1H-KMR-Spektren charakterisiert.

Durch Umsetzung von Phosphoryltrihalogeniden mit Ammoniak in Äther konnte Phosphorylchloridfluorid-amid, Phosphoryldichlorid-amid und das bereits bekannte Phosphoryldifluorid-amid gewonnen werden. Phosphorylchloridfluorid-amid reagiert mit Phosphorpentachlorid zu N-Trichlorphosphoranyliden-phosphoryl-chloridfluoridamid, O = PFClN = PCl3. Die neuen Verbindungen werden durch ihre Elementaranalyse, IR-Spektren und 31P-, 19F- und 1H-KMR-Spektren charakterisiert.