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  • Diazaboroles  (3)
  • Chromium complexes  (2)
  • Metallophosphaalkenes  (2)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1145-1152 
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Halogens ; Isocyanides ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of differently substituted 2-chloro-, 2-fluoro- and 2-iodo-2,3-dihydro-1H-1,3,2-diazaboroles have been prepared by various methods. 1,3-Di-tert-butyl-2-fluoro-2,3-dihydro-1H-1,3,2-diazaborole (3a), 1,3-di-tert-butyl-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5a), 1,3-bis(2,6-dimethyl-phenyl)-2-chloro-2,3-dihydro-1H-1,3,2-diazaborole (5b), 2-chloro-4,5-dimethyl-1,3-dineopentyl-2,3-dihydro-1H-1,3,2-diazaborole (5c), and 1,3-di-tert-butyl-2-iodo-2,3-dihydro-1H-1,3,2-diazaborole (6a) were formed from the corresponding lithiated Z-1,2-diaminoethenes, by treatment with BF3·OEt2, BCl3, or BI3 in n-hexane. Compounds 3a, 5a, and 5b are also available by sodium amalgam reduction of the adduct (tBu)(BF3)N=CH-CH=N(BF3)(tBu) (2a), and the borolium salts [RNa=CH-CH=Nb(R)BCl2]X (Na-B) (4a: R = tBu, X = BCl4 and 4b: R = 2,6-Me2C6H2, X = Cl) respectively. The iodo derivative (2,6-Me2C6H2)-Na-CH=CH-Nb(2,6-Me2C6H2)BI (Na-B) (6b) was synthesized in a redox reaction between the 1,4-diazabutadiene 1b and BI3. The novel compounds were characterized by 1H-, 11B- and 13C-NMR spectroscopy, as well as by an X-ray structure analysis of 6b.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1998/98047_s.pdf or from the author.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 491-497 
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Hydrides ; Tin ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (4a) and 1,3-bis(2,6-dimethylphenyl)-2,3-dihydro-1H-1,3,2-diazaborole (4b) were formed by the reaction of the corresponding 2-bromo or 2-iodo derivatives 1a and 2b with LiAlH4. Treatment of 1a with n-butyllithium afforded 2-n-butyl-1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (5a), whereas 1,3-di-tert-butyl-2-cyano-2,3-dihydro-1H-1,3,2-diazaborole (3a) was converted into the 2-tert-butyl derivative 6a or the 2-ethynyl-1,3,2-diazaborole 7a by means of tert-butyllithium or by the ethylenediamine adduct of lithium acetylide. Similarly, 1,3-di-tert-butyl-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8a) and 1,3-bis(2,6-dimethylphenyl)-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8b) were accessible from 1a or 2b and trimethylstannyllithium. In the complex 9a the compound 3a serves as an η1 ligand towards the [Cr(CO)5] unit via the cyano group. These novel compounds were characterized by 1H-, 11B-, 13C-, and 119Sn-NMR spectroscopy, as well as by X-ray structure analyses of 4b, 8a, and 9a.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1553-1557 
    ISSN: 0009-2940
    Keywords: Phosphido complexes ; Phosphaalkenes ; Diphosphiranes ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition-Metal-Substituted Diphosphenes, XXVII[1]. - Synthesis and Structure of the Diphosphirane (η5-C5Me5)(CO)2Fe-PH[Cr(CO)5(η5-C5Me5)(CO)2FePH2 (5), prepared from (η5-C5Me5)(CO)2Fe-P(SiMe3)2 and ethanol, reacts with one equivalent of ClP = C(SiMe3)2 to give the diphosphirane (η5-C5Me5)(CO)2FePH (8). Compound 8 is converted into the iron chromium complex [(η5-C5Me5)(CO)2Fe-H]Cr(CO)5(9). In contrast, the reaction of 5 with two equivalents of ClP=C(SiMe3)2 results in the formation of the cyclotri-phosphane [(η5-C5Me5)(CO)2Fe-[CH(SiMe3)2] (12). The molecular structure of 9 is elucidated by single-crystal X-ray analysis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0009-2940
    Keywords: Boron ; Diazaboroles ; Carbenes ; Heterocycles ; Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Bromo-2,3-dihydro-1H-1,3,2-diazaboroles (3a-c) were synthesized by cyclocondensation of dilithiated 1,4-diazabutadienes (5a-c) with boron tribromide in hexane. 3a was also obtained by sodium amalgam reduction was conducted in ether solvents, diboroxane (2) resulted as the main product. Compound 3a and 1,3-dialkyl-4,5-dimethylimidazol2-ylidenes (6a, b) underwent halide displacement to afford the borolylimidazolium salts 7a, b. Compounds 2, 3a-c, and 7a, b were characterized by elemental analyses and spectroscopic methods (1H, 11B, 13C NMR; Ir; MS). The molecular structures of 2 and 7a were established by single-crystal X-ray diffraction analyses.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0009-2940
    Keywords: Diphosphapropenes ; CH insertion ; Diphosphiranes ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rearrangements of the Metallodiphosphapropenes (η5-C5Me5)(CO)2FeP(SiMe3  -  P = C(R)(SiMe3) (R = SiMe3, Ph)Heating of a methylcyclohexane solution of (η5-C5Me5)-(CO)2FeP(SiMe3)  -  P = C(SiMe3)2 (1a) gives rise to the insertion of the P = C moiety into the CH bond of a ring methyl group with formation of the chelate complex η5-ηC5Me4CH2P-[CH(SiMe3)2]P(SiMe3)Fe(CO)2 (2) which is converted into the pentacarbonylchromium derivative [5-C5Me4CH2P[CH-(SiMe3)2]P(SiMe3)[Cr(CO)5]Fe(CO)2] (3). In contrast, a similar treatment of (5-C5Me5)(CO)2FeP(SiMe3)  -  P = C(Ph)(SiMe3) (1 b) furnishes the diphosphirane (5-C5Me5)(CO)2FeP  -  C(Ph)-SiMe3)  -  P (SiMe3) (5). By chromatography of its (CO)5Cr adduct 6, the P  -  Si bond is hydrolyzed to give the (diphosphirane)-chromium complex [(5-C5Me5)(CO)2FeP-C(Ph)(SiMe3)P(H)]-Cr(CO)5 (8). The molecular structures of 3 and 8 are determined by single-crystal X-ray analysis.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0044-2313
    Keywords: Metallophosphaalkenes ; Transition Metal Complexes ; X-Ray Structure Analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Transition-Metal Substituted Phosphaalkenes and Acyl Phosphanes. 31 [1] Reactivity of (η5-C5Me5)(CO)2FeP = C(NMe2)2 towards Tin Dichloride. X-Ray Structure Analysis of {(η5-C5Me5)[η1-(Me2N)2C = P—P = C(NMe2)2](CO)2Fe}+{[Me2N)2C]2P}+(FeCl4)2-Reaction of metallophosphaalkene (η5-C5Me5)(CO)2 · FeP = C(NMe2)2 (1) with anhydrous tin dichloride affords the salt-like compound {(η5-C5Me5)[η1-(Me2N)2C = P—P = C(NMe2)2] · (CO)2Fe}+{[(Me2N)2C]2P}+(FeCl4)2- 5 which is characterized by single crystal X-ray analysis and spectra (IR, 1H, 31P-NMR).
    Notes: Die Reaktion des Metallophosphaalkens (η5-C5Me5(CO)2FeP = C(NMe2) 2 (1) mit wasserfreiem Zinndichlorid liefert die salzartige Verbindung {(η5-C5Me5)[η1-(Me2N)2 · C = P—P = C(NMe2)2](CO)2Fe}+{[(Me2N)2C]2P}+(FeCl4)2-5, die durch Einkristall-Röntgenstrukturanalyse und Spektren (IR, 1H, 31P-NMR) charakterisiert wird.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 271-288 
    ISSN: 0570-0833
    Keywords: metallophosphaalkenes ; phosphaalkenes ; transition metal compounds ; Metallophosphaalkenes ; Phosphaalkenes ; Transition metals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemistry of low-valent organophosphorus compounds such as phosphaalkenes and phosphaalkynes has undergone rapid development in the last two decades. This development also includes the coordination chemistry of these species, which can act as versatile ligands in metal complexes. Metallophosphaalkenes are compounds in which one or more of the organic substituents on the P=C unit is replaced by a transition metal complex fragment. Metallophosphaalkenes have emerged from an existence as laboratory curiosities to become a link between main group and organometallic complex chemistry. The great richness of their chemistry not only mirrors the specific properties of the individual building block, but also shows novel and individual traits. Particular examples are cycloadditions of these electron-rich heteroalkenes with electron-deficient alkenes, alkynes, azo, and diazo compounds. These often lead to novel types of reaction and compounds. Metallophosphaalkenes are also important as intermediates in all metal-assisted cyclooligomerizations of phosphaalkynes.
    Additional Material: 5 Ill.
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