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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1625-1631 
    ISSN: 0044-2313
    Keywords: Selenium diimides ; Stannylenes ; Redox reactions ; Spiro-tin compounds ; Tin-Tin bond ; X-Ray analysis ; NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaktion von N,N′-Dialkylselendiimiden mit Bis(amino)stannylenen  -  Bildung einer Zinn-Zinn-BindungN,N′-Dialkylselendiimide 1, R(NSeN)R [R = tBu (a), tOct (b)], reagieren mit Bis(amino)stannylenen wie 1,3-Di-tert-butyl-4,4-dimethyl-1,3,4,2λ2-diazasilastannetidin (2), 1,3-Di-tert-butyl-4,4,5,5-tetramethyl-1,3,4,5,2λ2-diazadisilastannolidin (3), Bis[tert-butyl(trimethylsilyl)amino]stannylen (4) und Bis[bis(trimethylsilyl)amino]stannylen (5) im Verhältnis 1 : 1. Die Produkte sind entweder die Spiro-Zinn(IV)-Verbindungen 6 und 7, bestehend aus dem entsprechenden cyclischen Bis(amino)stannylen und einem viergliedrigen -Ring, oder die analogen viergliedrigen 1,2,4,3-Selenadiazastannetidin-Ringe 8 und 9 mit den Zinngebundenen Aminogruppen. Nur im Fall des viergliedrigen cyclischen Stannylens 2 reagieren auch zwei Äquivalente von 2 mit 1 a zu dem Polycyclus 10: Zwei Moleküle 2 sind über eine Zinn-Zinn-Bindung verknüpft, die durch die NSeN Gruppierung verbrückt ist, so daσ ein fünfgliedriger -Ring mit engen Sn—Se Kontakten entsteht. Alle Produkte wurden mittels Multikern NMR-Spektroskopie in Lösung charakterisiert (1H, 13C, 15N, 29Si, 77Se, 119Sn NMR), und die Molekülstruktur des Polycyclus 10 wurde mittels Einkristall-Röntgenstrukturanalyse bestimmt [monoklin; Raumgruppe C2/c; a = 3 294,1(3), b = 1 321,5(3), c = 1 855,9(2) pm und β = 98,02(2)°].
    Notes: N,N′-Dialkyl selenium diimides 1, R(NSeN)R [R = tBu (a), tOct (b)], react with bis(amino)stannylenes such as 1,3-di-tert-butyl-4,4-dimethyl-1,3,4,2λ2-diazasilastannetidine (2), 1,3-di-tert-butyl-4,4,5,5-tetramethyl-1,3,4,5,2λ2-diazadisila-stannolidine (3), bis[tert-butyl(trimethylsilyl)amino]stannylene (4) and bis[bis(trimethylsilyl)amino]stannylene (5) in a 1 : 1 ratio. The products are either the spiro-tin(IV) compounds 6 and 7, consisting of the respective cyclic bis(amino)stannylene and a four-membered ring, or the analogous four-membered 1,2,4,3-selenadiazastannetidine rings 8 and 9 with the amino groups linked to the tin atom. Only in the case of the four-membered cyclic stannylene 2, two equivalents of 2 may also react with 1 a to a polycyclic compound 10: Two molecules of 2 are linked by a tin-tin bond and this bond is bridged by the NSeN group, to give a five-membered ring with close Sn—Se contacts. All products were characterized by multinuclear magnetic resonance spectroscopy (1H, 13C, 15N, 29Si, 77Se, 119Sn NMR) in solution, and the molecular structure of the polycyclic compound 10 was determined by single crystal X-ray analysis [monoclinic; space group C2/c; a = 3 294.1(3), b = 1 321.5(3), c = 1 855.9(2) pm and β = 98.02(2)°].
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 2075-2082 
    ISSN: 0044-2313
    Keywords: Alkaline-earth cyanamide cyanides ; syntheses ; crystal structure ; anti-NiAs structure type ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ba2(CN2)(CN)2 and Sr2(CN2)(CN)2 - the First mixed Cyanamide CyanidesThe mixed cyanamide-cyanides M2(CN2)(CN)2 (M = Ba, Sr) were synthesized by the reaction of Ba2N and SrCO3, respectively, with HCN at 630°C. The crystal structure of Ba2(CN2)(CN)2 was determined from single-crystal X-ray investigations at room temperature and -100°C; the isostructural Sr2(CN2)(CN)2 was refined using powder methods (P63/mmc; Ba2(CN2)(CN)2: a = 1 066.52(5) pm, c=696.82(3) pm; Sr2(CN2)(CN)2: a = 1 035.91(1) pm, c = 664.23(1) pm; Z = 4). The crystal structure is a partially filled defect variant of the anti-NiAs structure type with a distorted hexagonal close packed arrangement of M2+-ions. All CN22- and one quarter of the CN- ions occupy 3/4 of the octahedrally coordinated interstices, the remaining cyanide anions are located at 3/8 of the tetrahedral sites. In the crystal structure the CN- are coordinated to the cations both end-on and side-on. All anions can be distinguished by vibrational spectroscopy.
    Notes: Die gemischten Cyanamid-cyanide M2(CN2(CN)2 (M = Ba, Sr) wurden durch Umsetzung von Ba2N bzw. SrCO3 mit HCN bei 630°C synthetisiert. Die Bestimmung der Kristallstruktur von Ba2(CN2)(CN)2 erfolgte anhand von Röntgen-Einkristalluntersuchungen bei Raumtemperatur bzw. -100°C, die Struktur des isotypen Sr2(CN2)(CN)2 wurde aus Pulverdaten verfeinert (P63/mmc, Ba2(CN2)(CN)2: a = 1 066,52(5) pm, c = 696,82(3) pm; Sr2(CN2)(CN)2: a = 1 035,91(1) pm, c = 664,23(1) pm; Z = 4). Die Kristallstruktur läßt sich als partiell aufgefüllte Defektvariante des anti-NiAs-Typs mit einer verzerrt hexagonal dichten Packung von M2+-Ionen auffassen. Sämtliche CN22-- und ein Viertel der CN--Ionen besetzen 3/4 der Oktaederlücken, die restlichen CN--Einheiten 3/8 der Tetraederlücken. Im Kristallverband sind die CN--Ionen sowohl end-on als auch side-on an die Kationen koordiniert. Die Anionen sind schwingungsspektroskopisch unterscheidbar.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 724-728 
    ISSN: 0044-2313
    Keywords: Nitrosyl complexes ; halfsandwich compounds ; 1,3-dichalcogena-2-metalla-[3]ferrocenophanes, crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New 1,1′-Ferrocene Dichalcogenato Complexes of Ruthenium and OsmiumBoth trinuclear 1,1′-ferrocene dichalcogenato complexes(1) such as fc(E[MLn])2 (1a - c) (with [MLn] = Ru(CO)2Cp*; E = S, Se, Te) and dinuclear [3]ferrocenophane derivatives of the type fcE2[MLn] (with [MLn] = Ru(CO)(η6-C6Me6) (2a, b), Ru(NO)Cp* (3a, b) (E = S, Se) or Os(NO)Cp* (4a - c) (E = S, Se, Te)) were synthesized and characterized by their IR-, 1H- and 13C NMR spectra as well as their mass spectra. The molecular structure of fcS2[Os(NO)Cp*] (4a) was determined by an X-Ray structure analysis; the long Fe…Os distance of 431.1(1)pm excludes any direct bonding interactions.
    Notes: Es wurden sowohl dreikernige 1,1′-Ferrocendichalkogenato-Komplexe(1) wie fc(E[MLn])2 (1 a - c) (mit[MLn] = Ru(CO)2Cp*; E = S, Se, Te) als auch zweikernige [3]Ferrocenophan-Derivate des Typs fcE2[MLn] (mit[MLn] = Ru(CO)(η6-C6Me6) (2a, b), Ru(NO)Cp* (3a, b) (E = S, Se) oder Os(NO)Cp* (4a - c) (E = S, Se, Te)) synthetisiert und anhand ihrer IR-, 1H- und 13C-NMR-Spektren sowie ihrer Massenspektren charakterisiert. Die Molekülstruktur von fcS2[Os(NO)Cp*] (4a) wurde durch eine Röntgenstrukturanalyse bestimmt; der lange Fe…Os Abstand von 431,1(1)pm schließt direkte Bindungswechselwirkungen aus.
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  • 4
    ISSN: 0044-2313
    Keywords: Ferrocene derivatives ; Sulfinylimides ; Sulfurdiimides ; Variable temperature NMR spectroscopy ; Crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ferrocenyl-sulfinylimid und Diferrocenyl-schwefeldiimid, Fc—NSO und Fc(NSN)FcDie Umsetzung von Ferrocenylamin, Fc—NH2 (1), mit Thionylchlorid bzw. Schwefeldichlorid in Hexanlösung in Gegenwart von Triethylamin ergibt die Titelverbindungen Fc—NSO (2) und Fc(NSN)Fc (3). Beide Produkte wurden auch bei der Reaktion des silylierten Ferrocenylamins, Fc—NH(SiMe3) (1b), mit Thionylchlorid erhalten. Das Ferrocenyl-sulfinylimid 2 wurde durch Umsetzung mit dem Lithiumderivat silylierter Amine, LiN(SiMe3)R (R = Fc, tBu, SiMe3) in Schwefeldiimide wie Fc(NSN)Fc (3) und Fc(NSN)R (R = tBu, (4a), SiMe3 (4b)) umgewandelt. Die neuen Ferrocenylverbindungen 2-4 wurden anhand ihrer NMR-Spektren charakterisiert, und ihr elektrochemisches Verhalten wurde untersucht. Die Molekülstruktur von Fc—NSO (2) wurde mit Hilfe einer Röntgenstrukturanalyse bestimmt; das Sulfinylimid liegt in der Z-Konfiguration vor, und die  -  NSO Gruppe liegt in der Ebene des Cyclopentadienylringes, an den sie gebunden ist.
    Notes: Abbreviations and Nomenclature: Fc = η1-ferrocenyl, CpFe(C5H4-); Cp = η5-cyclopentadienyl, η5-C5H5. Compounds containing the  - NSO group are designated as either thionylimides, sulfinylimides or N-sulfinylamines. The systematic name is imido oxo sulfuranes(IV). The reactions of ferrocenylamine, Fc—NH2 (1), with thionyl chloride and sulfur dichloride in hexane solution in the presence of triethylamine lead to the title compounds Fc—NSO (2) and Fc(NSN)Fc (3), respectively, 2 and 3 have also been obtained in reactions of the silylated ferrocenylamine, Fc—NH(SiMe3) (1b), with thionyl chloride. The ferrocenyl sulfinylimide 2 has been converted to sulfurdiimides such as Fc(NSN)Fc (3) and Fc(NSN)R (R = tBu (4a), SiMe3 (4b)) by reaction with the lithium derivative of silylated amines, LiN(SiMe3)R (R = Fc, tBu, SiMe3). The new ferrocenyl compounds 2-4 have been characterized by their NMR spectra, and their electrochemical behaviour has been studied. The molecular structure of Fc—NSO (2) has been determined by an X-ray structure analysis; the sulfinylimide has the Z configuration, and the  - NSO group is coplanar with the cyclopentadienyl ring to which it is attached.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1599-1608 
    ISSN: 0044-2313
    Keywords: Cyclophosphazenes ; [3]ferrocenophanes ; 1,1′-ferrocene-dichalcogenato compounds ; NMR spectra ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Ferrocenol and 1,1′-Ferrocendiol with Cyclotriphosphazenes, P3N3F6 and P3N3Cl6The hexahalogeno-cyclotriphosphazenes, P3N3X6 (X = F (1 a), Cl (1 b)), react with ferrocenol (FcOH) in a molar ratio 1 : 1 to give the ferrocenoxy derivatives, FcO[P3N3X5] (X = F (3 a), Cl (3 b)); in an analogous manner the tetrameric ring P4N4Cl8 (2 b) is converted to FcO[P4N4Cl7] (4 b). Abkürzungen: Fc = Ferrocenyl, (C5H5)Fe(C5H4-); fc = 1,1′-ferrocendiyl, Fe(C5H4-)2; rc = 1,1′-ruthenocendiyl, Ru(C5H4-)2. Fluorphosphazene werden mit a, Chlorphosphazene mit b gekennzeichnet. With 1,1′-ferrocenediol, (fc(OH) 2), the cyclo triphosphazenes react in a molar ratio 1 : 1 to produce fcO 2[P 3 N 3 X 4] (X = F ( 5 a), Cl ( 5 b)). According to the x-ray structure analysis, the 1,1′-ferrocenediolato group in 5 a , b is bound to two different phosphorus atoms. On the contrary, the 1,1′-ferrocenedithiolato- and 1,1′-ferrocenediselenolato units in fcS 2[P 3 N 3 X 5] (X = F ( 6 a), Cl ( 6 b)) and fcSe 2[P 3 N 3 X 5] (X = F ( 7 a), Cl ( 7 b)) are attached to only one phosphorus atom, and spirocyclic 1,3-dichalcogena-2-phospha-[3]ferrocenophanes are formed. All new products have been characterized on the basis of their 1 H, 13 C and 31 P NMR as well as EI mass spectra. The molecular structures of 5 a , b and 6 a have been determined by x-ray structure analyses.
    Notes: Die Hexahalogen-cyclotriphosphazene, P3N3X6 (X = F (1 a), Cl (1 b)), reagieren mit Ferrocenol, FcOH, im Molverhältnis 1 : 1 unter Bildung der Ferrocenoxy-Derivate FcO[P3N3X5] (X = F (3 a), Cl (3 b)); der tetramere Ring P4N4Cl8 (2 b) bildet in analoger Weise FcO[P4N4Cl7] (4 b). 1,1′-Ferrocendiol, fc(OH)2, setzt sich mit P3N3X6 im Molverhältnis 1 : 1 zu fcO2[P3N3X4] (X = F (5 a), Cl (5 b)) um; nach der Röntgenstrukturanalyse ist der 1,1′-Ferrocendiolato-Rest in 5 a, b an zwei verschiedene Phosphoratome gebunden. Dagegen werden die 1,1′-Ferrocendithiolat- und 1,1′-Ferrocendiselenolat-Reste in fcS2[P3N3X4] (X = F (6 a), Cl (6 b)) bzw. fcSe2[P3N3X4] (X = F (7a), Cl (7 b)) jeweils nur an ein Phosphoratom angekoppelt, so daß spirocyclische 1,2-Dichalkogena-2-phospha[3]ferrocenophane entstehen. Alle neuen Produkte wurden anhand ihrer 1H-, 13C- und 31P-NMR-Spektren und der EI-Massenspektren charakterisiert; für 5 a, b und 6 a wurde die Molekülstruktur durch Röntgenstrukturanalyse bestimmt.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 701-704 
    ISSN: 0009-2940
    Keywords: N-Silyl amides ; Precursor ; 14N-NMR ; Titanium ; Tungsten ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of hexachlorodisilazanyllithium (Cl3Si)2NLi (1), with TiCl4 leads selectively to the novel fully chlorinated amides (Cl3Si)2NTiCl3 (2) or [(Cl3Si)2N]2 TiCl2 (3), respectively, depending on the molar ratio of the starting materials. The analogous reaction of 1 with WCl6 yielded the amide imide Cl3SiN=W(Cl3)N(SiCl3)2 (5) by elimination of SiCl4. The relative amounts of the starting materials had no effect on the formation of 5. 14/15N- and 29Si-NMR data on the starting materials and products show significantly different effects, when compared with those of analogous N-trimethylsilyl derivatives, due to the lower energy of the electrons in the N—Si and N—M ß bonds. The crystal structure of 5 (triclinic, space group P1) was determined by X-ray structure analysis.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 557-560 
    ISSN: 0009-2940
    Keywords: Halfsandwich iridium complexes ; cyclo-Sulfido ligands ; Chalcogen-bridged iridium complexes ; Cubane clusters ; Iridium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photolysis or thermolysis of Cp*Ir(CO)2 (1) in the presence of excess sulfur (S8) gives Cp*Ir(CO)(S4) (2a) which is further decarbonylated to [Cp*Ir(μ-S4)]2 (4a). The analogous reaction of 1 with excess selenium leads to Cp*2Ir2(μ-Se)(μ-Se4) (6b). In the case of limited chalcogen supply, the products are [Cp*Ir(CO)(μ-E)]2 [E = S (3a), Se 3b)] and [Cp*Ir(μ-E)]4 [E = S (5a), Se (5b)]. A stepwise formation of the pseudocubane clusters 5a,b from dinuclear precursors is assumed. The solid-state structure of 2a has been determined by X-ray crystallography.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 147-153 
    ISSN: 0009-2940
    Keywords: 1,1-Organoboration ; 1-Alkynylsilanes ; 1,2,5-Azoniasilaboratoles, 2,5-dihydro-, organo-substituted ; Heterocyclic synthesis ; Multinuclear NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Alkynyl(diethylamino)dimethylsilanes [CC̊: R = Me (1a), nBu (1b), SiMe3 (1c)] react with triethylborane stereoselectively by 1,1-ethyloboration to give the alkenes with the boryl and silyl group in cis-positions at the C=C bond. Owing to the strongly intramolecular coordinative N-B bond, these products are 2,5-dihydro-1,2,5-azoniasilaboratoles (2a-c). Protic reagents such as azoles (indole, pyrazole, imidazole, triazole, indazole, benzotriazole) react with 2 to give diethylamine and the respective N-azolyl derivatives 3-8 which contain tetracoordinate boron in the case of 4-8. Compound 7, derived from indazole, was characterized by an X-ray analysis. With ethanol, the corresponding 2,5-dihydro-1,2,5-oxoniasilaboratoles 9 are obtained. Treatment of 2 with water affords 1,2,5-oxasilaborolanes 11, presumably via an intermediate 10 with the structure of a 2,5-dihydro-1,2,5-oxoniasilaboratole. All products were characterized by their 1H-, 11B-, 13C-, 15N-, and 29Si-NMR data.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1349-1352 
    ISSN: 0009-2940
    Keywords: Heterocycles ; 1,1-Organoboration ; Disilanes ; 1- Alkynylsilanes ; NMR spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Di-1-propynyl-tetramethyldisilan (1) reacts with triorganoboranes R3B [R = Et (2a), CH2Ph (2c), 2-thienyl (2d)], 9-ethyl-9-borabicyclo[3.3.1]nonane (3), and diethyl(N-pyrrolyl)borane (4) by twofold 1,1-organoboration to give selectively the respective organo-substituted 1,2-dihydro-1,2,5-disilaborepines 5a-d,6, and 7 in high yields. The compounds 5-7 were characterized by 1H-, 11B-, 13C-, and 29Si-NMR spectroscopy in solution. The molecular structures of the distance 1 and of the heterocycle 5c were determined by X-ray structure analysis.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 299-303 
    ISSN: 0044-2313
    Keywords: Rhenium complexes ; rhenium trichalcogenido, -tetrachalcogenido complexes ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Rhenium Complexes Containing Trichalcogenido and Tetrachalcogenido Chelate LigandsThe reactions of Cp*ReCl4 with polychalcogenide salts such as Na2S4 or (NEt4)2Se6 lead initially to the violet trichalcogenido chelate complexes Cp*ReCl2(E3) (E = S (3a), Se (3b)) which, due to their functional chloro ligands, can be used as intermediates for further reactions. Upon hydrolysis in moist solvents or aminolysis with tert. butylamine 3a, b are converted into the tetrachalcogenido chelate complexes Cp*Re(O)(E4) (E = S (4a), Se (4b)) and Cp*Re(NtBu)(E4) (E = S (5a), Se (5b)), respectively. X-Ray structure analyses were carried out for the three mononuclear cyclo-oligoselenido compounds 3b-5b. It appears that the size of the Se2-n chelate ring (n = 3 or 4) essentially depends on steric factors within the coordination sphere of rhenium.
    Notes: Die Reaktionen von Cp*ReCl4 mit Polychalkogenid-Salzen wie Na2S4 oder (NEt4)2Se6 führen zunächst zu den violetten Trichalkogenido-Chelatkomplexen Cp*ReCl2(E3) (E = S (3a), Se (3a), die aufgrund der funktionellen Chloroliganden als Zwischenstufen bei weiteren Reaktionen verwendet werden können. Bei Hydrolyse in feuchten Solvenzien oder Aminolyse mit tert. Butylamin werden 3a, b in die Tetrachalkogenido-Chelatkomplexe Cp*Re(O)(E4) (E = S (4a), Se (4b) bzw. Cp*Re(NtBu)(E4) (E = S (5a), Se (5b) umgewandelt. Für die drei einkernigen cyclo-Oligoselenido-Verbindungen 3b-5b wurden Röntgenstrukturanalysen durchgeführt. Es scheint, daß die Größe des Se2-n-Chelatrings (n = 3 oder 4) im wesentlichen von sterischen Faktoren innerhalb der Koordinationssphäre des Rheniums abhängt.
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