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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: Heterobimetallic complexes ; Iron complexes ; Platinum complexes ; Silyl complexes ; Phosphido bridges ; Hydrido complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Silyl Complexes, 48[1]. - Synthesis of the New Heterobimetallic Dinuclear Silyl Complexes (OC)3(R3Si)-Fe(μ-PR′R″)Pt(1,5-COD)(Fe-Pt), Phosphane Exchange Reactions of (OC)3(R3Si)Fe(μ-PR′R″)Pt(PPh3)2(Fe-Pt), and Preparation of the Dihydrido complexes [(OC)3Fe(μ-PPh2)(μ-H)2Pt(PR3)2][BF4](Fe-Pt)The dinuclear, silyl-substituted complexes (OC)3(R3Si)Fe(μ-PR′r″)Pt(1,5-COD) (1) [μ-PR′R″ = PPh2, PCY2, PHPh; SiR3 = SiPh3, Si(OMe)3] were prepared in high yields by the oxidative addition of the hydrido complexes (OC)3(PHR′R″)Fe(H)-SiR3 to Pt(1,5-COD)2. Upon reaction of (OC)3(R3Si)Fe(μ-PR′R″)Pt(PPh3)2 [μ-PR′R″ = PPh2, PHCy; SiR3 = SiPh3, SiPh2Me, SiPhMeCl, Si(OMe)3] with two equivalents of PR‴3 (PMe3, PBu3, PEt3) or with one equivalent of chelating di-phosphanes (vdpp, dppe, dppm) both PPh3 ligands are displaced, and (OC)3(R3Si)Fe(μ-PR′R″)Pt(PR‴3)2 or (OC)3(R3Si)-Fe(μ-PR′R″)Pt[(PPh2)2X] (X = C=CH2, C2H4, CH2) are formed, respectively. When one equivalent of PMe3 is used, only the PPh3 ligand trans to the μ-PPh2 bridge is substituted, and (OC)3(Ph3Si)Fe(μ-PPh2)Pt(PPh3)(PMe3 is formed. The 1,5-COD ligand in 1 is displaced by P(OR)3 to give (OC)3-(Ph3Si)Fe(μ-PPh2)Pt[P(OR)3]2 (R = Me, Ph). The complexes (OC)3(Ph3Si)Fe(μ-PPh2)Pt(PMe3)2and (OC)3(Ph3Si)Fe(μ-PPh2)Pt[(PPh2)2C=CH2] were characterized by X-ray structure analysis. The short Fe-Si distances [233.0(2) and 235.6(3) pm] and the infrared v(CO) absorptions indicate that the Fe-Pt bonds are quite polar. Protonation of (OC)3(Me2-PhSi)Fe(μPPh2)Pt(PPh3)2 with CF3COOH gives the hydrido-bridged complex [(OC)3(Me2PhSi)Fe(μ-PPh2)(μ-H)Pt-(PPh3)2][O2CCF3]. Upon addition of an excess of HBF4 · Et2O to (OC)3(R3Si)Fe(μ-PPh2)Pt(PPh3)2 (R = Ph, OMe), (OC)3-Si)Fe(μ-PPh2)Pt[Pt[P(OMe)3]2 or (OC)3(Ph2MeSi)Fe(μ-PPh2)-Pt(dppe) R3SiF is split, and the corresponding μ-dihydrido complexes [(OC)3Fe(μ-PPh2)(μ-H)2Pt(PR3)2][BF4] are obtained.
    Additional Material: 2 Ill.
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