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Syntheses and Insertion Reactions of (η 2 ‐Aldehyde)zirconocene‐Supported (Hydrido)zirconocene Cation Systems
Author(s) -
Blaschke Ulrich,
Menges Frederik,
Erker Gerhard,
Fröhlich Roland
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199904)1999:4<621::aid-ejic621>3.0.co;2-p
Subject(s) - chemistry , adduct , moiety , yield (engineering) , nitrile , medicinal chemistry , hydride , stereochemistry , aldehyde , acetaldehyde , zirconium , crystal structure , metallocene , organic chemistry , catalysis , metal , materials science , ethanol , metallurgy , polymer , polymerization
Treatment of the [Cp 2 Zr(η 2 ‐acetaldehyde)/H(CH 3 )ZrCp 2 ] adduct 8 with B(C 6 F 5 ) 3 yields the dimetallabicyclic salt [Cp 2 Zr(μ‐η 1 ‐O:η 2 ‐C,O‐OCHMe)(μ‐H)(ZrCp 2 )] + [CH 3 B(C 6 F 5 ) 3 ] − 18b . Similarly, hydride abstraction from the related neutral dimetallabicyclic [Cp 2 Zr(OCHR)/H 2 ZrCp 2 ] adducts 11 (R = CH 3 ) or 14 (R = C 2 H 5 ) with B(C 6 F 5 ) 3 yields the systems [Cp 2 Zr(μ‐η 1 ‐O:η 2 ‐C,O‐OCHR)(μ‐H)(ZrCp 2 )] + [HB(C 6 F 5 ) 3 ] − ( 18a , c ) and the reaction of B(C 6 F 5 ) 3 with [Cp 2 Zr(OCHCH 2 Ph)/H(PhCH 2 )ZrCp 2 )] + 17 gives [Cp 2 Zr(μ‐η 1 ‐O:η 2 ‐C,O‐(OCHCH 2 Ph)(μ‐H)ZrCp 2 ] + [PhCH 2 B(C 6 F 5 ) 3 ] − 18d . A variety of nitriles R 2 –C≡N (R = CH 3 , CMe 3 , p ‐tolyl, or ethyl) cleanly reacts with the cations 18 by addition of the Zr 2 (μ‐H) moiety to the nitrile functionality to yield the respective aldiminium‐bridged cations [Cp 2 Zr(μ‐η 1 ‐O:η 2 ‐C,O‐(OCHR 1 )(μ‐N=CHR 2 )ZrCp 2 ] + ( 21 – 24 ). Complex 24d (R 1 = PhCH 2 , R 2 = C 2 H 5 ) was characterized by an X‐ray crystal structure analysis. Similarly, treatment of the systems 18a – d with isocyanates RN=C=O (R = CMe 3 , SiMe 3 , p ‐tolyl, or adamantyl) gave the related μ‐formamidato complexes 27 – 30 .