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  • 1
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1337-1341 
    ISSN: 0947-6539
    Keywords: NMR spectroscopy ; silazanes ; tin ; titanium ; zirconium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of hexamethyldisilazane with TiCl4 in CH2Cl2 leads to the formation of [(Me3SiNTiCl2)8] (3). According to the crystal structure analysis, 3 is an octameric titanium trimethylsilylimido chloride. The mechanism of the formation of 3 was studied in detail by means of time-dependent 14N NMR spectroscopy. [(Me3Si)2NTiCl3] was identified as an intermediate during the formation of 3. Two by-products were identified: [(NH4)2TiCl6] and the hitherto unknown bis(trimethylsilyl)ammonium salt [(Me3Si)2NH2]+[Ti2Cl9]- (5). According to the crystal structure analysis, protonation of hexamethyldisilazane to give the cation of 5 causes a significant lengthening of the Si-N bond from 173.5 to 186 pm. Other tetravalent metal chlorides, such as ZrCl4 and SnCl4, also reacted with hexamethyldisilazane to yield bis(trimethylsilyl)ammonium salts. However, the constitution of the corresponding anions differs significantly. In the case of ZrCl4, an anionic chlorotrimethylsilylimidozirconate (6) [(Me3Si)2NH2]+2-[{Cl3ZrCl3Zr(Cl)(NSiMe3)}2]2- was obtained, while SnCl4 reacted to give a novel spiro anion [N(SnCl3)2(SnCl2)4-(NSiMe3)2NH)2]- together with the bis(trimethylsilyl)ammonium ion in 7; this anion is the first species containing a tetrastannylated nitrogen.
    Additional Material: 8 Ill.
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  • 3
    ISSN: 1434-1948
    Keywords: Sandwich complexes ; Iron ; Tin ; NMR spectroscopy ; Mössbauer spectroscopy ; Electrochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 1,1′-bis(chlorostannyl)-substituted ferrocenes Fe(C5H4-SnMe2Cl)2 (2), Fe(C5H4-SnMeCl2)2 (3) and Fe(C5H4-SnCl3)2 (4) were prepared, starting from 1,1′-bis(trimethylstannyl)ferrocene (1). Treatment of the chlorides with Li[AlH4] afforded the 1,1′-bis(hydridostannyl)-subsituted ferrocenes Fe(C5H4-SnMe2H)2 (5), Fe(C5H4-SnMeH2)2 (6) and Fe(C5H4-SnH3)2 (7), respectively. All complexes 1-7 were studied by 1H-, 13C-, and 119Sn-NMR spectroscopy with 1D and 2D techniques. The compounds 1-4 were investigated by temperature-dependent 119Sn- and 57Fe-Mössbauer spectroscopy. The electrochemistry of 1-5 gave evidence of reversible one-electron oxidation processes. The molecular structure of 1,1′-bis(trichlorostannyl)ferrocene (4) was determined by X-ray structural analysis, and there was no indication of intra- or intermolecular Sn···Cl···Sn interactions. This direct structural information proved to be consistent with both the Mössbauer and the solution NMR spectroscopic data.
    Additional Material: 5 Ill.
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  • 4
    ISSN: 0044-8249
    Keywords: Alkine ; Eisen ; Homogene Katalyse ; Sandwichkomplexe ; Zinn ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    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)°].
    Additional Material: 3 Ill.
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  • 6
    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.
    Additional Material: 9 Ill.
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  • 7
    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.
    Additional Material: 1 Ill.
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  • 8
    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.
    Additional Material: 4 Ill.
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  • 9
    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.
    Additional Material: 3 Ill.
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  • 10
    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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