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  • 1
    ISSN: 0009-2940
    Keywords: Anionic complexes ; Chromium complexes ; Manganese complexes ; Stannyl complexes ; Hydrido complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Stannyl Complexes, 9[1]. - Substitution Reactions of the Anionic Hydrido Complexes [(π-MeC5H4)-(CO)2MnH]- and [(π-Arene)(CO)2CrH]-The anionic hydrido complexes K[(π-MeC5H4)(CO)2MnH] (2c) and K[(π-arene)(CO)2CrH] (π-arene = C6H6, C6H5Me, 1,2,3-C6H3Me3, C6Me6, C6H5Ph, indan) (5a-f) are spontaneously formed on stirring THF solutions of the dianionic complexes K2 [(π-MeC5H4)(CO)2Mn] (1) or K2[(π-arene)(CO)2Cr] (4) at - 78°C. The dianionic complexes are obtained by potassium naphthalenide reduction of (π-MeC5H4)(CO)2MnL or (π-arene)(CO)2CrL (L = pyridine or THF). Reaction of 2c with Me3SnCl or Ph2SnCl2 yields the bis(stannyl) complexes Cp*(CO)2Mn(SnR3)2 (SnR3 = SnMe3, SnPh2Cl), while reactions with the „smaller“ stannanes Me2SnCl2 or Et2SnCl2 results in the SnR2-bridged complexes [Cp′(CO)2Mn]2(μ-SnR2)((Mn-Mn). The bis(stannyl) complexes (π-arene)(CO)2Cr(SnR2Cl)2 (R = Me, Ph) are obtained from 5 and R2SnCl2. However, the reaction is strongly influenced by steric effects: with Me2SnCl2, bis(stannyl) complexes are obtained for π-arene = C6H6, C6H5Me, 1,2,3-C6H3Me3, or C6Me6, with Ph2SnCl2 only for π-arene = C6H6 and C6H5Me. Reaction of the sterically demanding complexes K[(π-C6H5Ph)(CO)2CrH] or K[(π-indan)(CO)2CrH] with Ph2SnCl2 stops at the stage of the anionic stannyl complexes K[(π-arene)(CO)2Cr-SnPh2Cl].
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: β-Diketonates ; Metal alkoxides ; Sol-gel chemistry ; π-Arene complexes ; Chromium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal Complexes in Inorganic Matrices, 8[1]. - Chromium Tricarbonyl Complexes of Benzoylacetonate-Substituted Titanium-, Zirconium-, and Aluminium Alkoxides*Benzoylacetone (bzac-H) reacts with one equivalent of Al(OtBu)3 or Zr(OPr)4 to give the mono-substituted compounds (bzac)Al(OtBu)2 (1b) and (bzac)Zr(OPr)3 (1a), while with one equivalent of Ti(OtBu)4 or Zr(OtBu)4 the bis-substituted derivatives (bzac)2Ti(OtBu)2 (3c) and (bzac)2Zr(OtBu)2 (3d) are obtained. Upon heating in dibutyl ether, 1b disproportionates into (bzac)2Al(OtBu) (3b) and Al(OtBu)3. Thermal reaction of 1a, 3b, and 3c with Cr(CO)6 leads to metal complexes having a Cr(CO)3 moiety π-bonded to the phenyl group of the benzoylacetonate ligand.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Carbene complexes ; Stannyl complexes ; Chromium complexes ; Anionic complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Stannyl Complexes, 7[1]. - Preparation of Carbene Complexes (π1-Arene)(CO)2CrCR2 by the Reaction of the Anionic Stannyl Complexes [(π1-Arene)(CO)2CrSnPh3]- with R2CX2 or [R2CX]YCarbene complexes (π1-arene)(CO)2Cr=CR2 are formed in substitution/elimination reactions from the anionic stannyl complexes K[(π1-arene)(CO)2CrSnPh3] [π1-arene=C6H6 (1a), 1,3,5-Me3C6H3 (1b), 1,2,4,5-Me4C6H2 (1c)] C6Me6 (1d) and organic dihalides R2CX2 containing activated C - X bonds or ionic halides [R2CX]Y. Bis(stannyl) complexes (π1-arene)(CO)2Cr(SnPh3)2 (3) and hydrido(stannyl)complexes (π1-arene)(CO)2Cr(H)SnPh3 are formed as byproducts due to the reaction of the eliminated Ph3SnCl with the anionic starting complexes or electron transfer reactions, respectively. The portion and ratio of the byproducts is largely influenced by the steric properties of both the (π1-arene)(CO)2Cr fragment and the organic halide. Pyridinylidene complexes 2) are only obtained from 2-chloro-N1-methylpyridinium tetrafluoroborat with 1a - c, but not with 1d. With the sterically less demanding halides [R2N=C(H)Cl]Cl [NR2=NMe2, (n=3, 4)] or 3,3-dichloro-1,2-diphenylcyclopropene the carbene complexes (π1-arene)(CO)2Cr=C(H)NR2 or are obtained with all employed π1-arene ligands.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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