ISSN:
1434-1948
Keywords:
(η2-Aldehyde)zirconocene complexes
;
Metallaoxirane-stabilized group 4 metallocene hydride cations
;
Nitrile insertion
;
Isocyanate insertion
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Treatment of the [Cp2Zr(η2-acetaldehyde)/H(CH3)ZrCp2] adduct 8 with B(C6F5)3 yields the dimetallabicyclic salt [Cp2Zr(μ-η1-O:η2-C,O-OCHMe)(μ-H)(ZrCp2)]+[CH3B(C6F5)3]-18b. Similarly, hydride abstraction from the related neutral dimetallabicyclic [Cp2Zr(OCHR)/H2ZrCp2] adducts 11 (R = CH3) or 14 (R = C2H5) with B(C6F5)3 yields the systems [Cp2Zr(μ-η1-O:η2-C,O-OCHR)(μ-H)(ZrCp2)]+[HB(C6F5)3]- (18a, c) and the reaction of B(C6F5)3 with [Cp2Zr(OCHCH2Ph)/H(PhCH2)ZrCp2)]+17 gives [Cp2Zr(μ-η1-O:η2-C,O-(OCHCH2Ph)(μ-H)ZrCp2]+[PhCH2B(C6F5)3]-18d. A variety of nitriles R2-C≡N (R = CH3, CMe3, p-tolyl, or ethyl) cleanly reacts with the cations 18 by addition of the Zr2(μ-H) moiety to the nitrile functionality to yield the respective aldiminium-bridged cations [Cp2Zr(μ-η1-O:η2-C,O-(OCHR1)(μ-N=CHR2)ZrCp2]+ (21-24). Complex 24d (R1 = PhCH2, R2 = C2H5) was characterized by an X-ray crystal structure analysis. Similarly, treatment of the systems 18a-d with isocyanates RN=C=O (R = CMe3, SiMe3, p-tolyl, or adamantyl) gave the related μ-formamidato complexes 27-30.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
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