Coordination Behavior and Reactivity of α-Heterosubstituted Trimethylsilylalkynes at Titano- and Zirconocene

被引：11
作者：
Altenburger, Kai [1 ]
Baumann, Wolfgang [1 ]
Spannenberg, Anke [1 ]
Arndt, Perdita [1 ]
Rosenthal, Uwe [1 ]
机构：
[1] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany
来源：
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2014年 / 34期
关键词：
Metallocenes; Zirconium; Titanium; Alkynes; Regioselectivity; METAL-CARBON BONDS; C SINGLE BOND; ACETYLENE COMPLEXES; REGIOSELECTIVE REACTIONS; ADDITIONAL LIGANDS; CRYSTAL-STRUCTURE; ALKYNE COMPLEXES; BIS(TRIMETHYLSILYL)ACETYLENE; METALLACYCLES; DERIVATIVES;
D O I：
10.1002/ejic.201402851
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The coordination behavior of the a-donor-atom-substituted (trimethylsilyl) alkynes OC4H8N-C C-SiMe3 (2), EtO-C C-SiMe3 (3), and Me2P-C C-SiMe3 (4) towards group 4 metallocene generators [Cp2Ti(eta(2)-btmsa)] (1a), [Cp2Zr(py)(eta(2)-btmsa)] (1b), and [Cp-2*Ti(eta(2)-btmsa)] (1c) [Cp = eta(5)-cyclo-pentadienyl; btmsa = bis(trimethylsilyl)acetylene; py = pyridine; Cp* = eta(5)-pentamethylcyclopentadienyl] was investigated. By using 1a and 1b, metallacyclopropenes were obtained for alkyne 2, a titanacyclopentadiene for alkyne 3, and dimeric-stabilized metallacyclopropenes for alkyne 4. Employing the sterically demanding metallocene 1c resulted in monomeric metallacyclopropenes for alkynes 3 and 4. The reactivity of the obtained complexes towards CO2 and acetone was explored as well, thus leading to regioselective formation of metallafuranones and metalladihydrofurans.
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页码：5948 / 5957
页数：10
相关论文
共 49 条
  • [1] ACETYLENE DERIVATIVES OF TITANOCENE
    ALT, HG
    ENGELHARDT, HE
    RAUSCH, MD
    KOOL, LB
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (12) : 3717 - 3718
  • [2] ACETYLENE COMPLEXES OF TITANOCENE AS STARTING MATERIAL FOR 5-MEMBERED TITANACYCLES
    ALT, HG
    HERRMANN, GS
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1990, 390 (02) : 159 - 169
  • [3] Examples of Different Reactions of Benzylsulfanyl-Substituted Alkynes with Selected Complexes of TiII and CoI
    Altenburger, Kai
    Semmler, Julia
    Arndt, Perdita
    Spannenberg, Anke
    Meel, Matthias J.
    Villinger, Alexander
    Seidel, Wolfram W.
    Rosenthal, Uwe
    [J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013, 2013 (24) : 4258 - 4267
  • [4] Synthesis and Characterisation of Selected Group 4 Metallocene Complexes with 1,2-Bis(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-yl)acetylene
    Altenburger, Kai
    Arndt, Perdita
    Spannenberg, Anke
    Baumann, Wolfgang
    Rosenthal, Uwe
    [J]. EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013, (18) : 3200 - 3205
  • [5] Titanocene and Zirconocene Complexes with Diaminoacetylenes: Formation of Unusual Metallacycles and Fulvene Complexes
    Arias, Oscar
    Petrov, Alex R.
    Bannenberg, Thomas
    Altenburger, Kai
    Arndt, Perdita
    Jones, Peter G.
    Rosenthal, Uwe
    Tamm, Matthias
    [J]. ORGANOMETALLICS, 2014, 33 (07) : 1774 - 1786
  • [6] Reactions of titanium and zirconium derivatives of bis(trimethylsilyl)acetylene with tris(pentafluorophenyl)borane: A titanium(III) complex of an alkynylboranate
    Arndt, P
    Baumann, W
    Spannenberg, A
    Rosenthal, U
    Burlakov, VV
    Shur, VB
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (12) : 1414 - 1418
  • [7] Arndt P., 2003, ANGEW CHEM, V115, P1455
  • [8] Beweries T., 2007, ANGEW CHEM, V119, P7031
  • [9] Beweries T., 2012, SCI SYNTHESIS KNOWLE, P11
  • [10] Tandem Si-C and C-H activation for decamethylhafnocene and bis(trimethylsilyl)acetylene
    Beweries, Torsten
    Burlakov, Vladimir V.
    Bach, Marc A.
    Peitz, Stephan
    Arndt, Perdita
    Baumann, Wolfgang
    Spannenberg, Anke
    Rosenthal, Uwe
    Pathak, Biswarup
    Jemmis, Eluvathingal D.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (36) : 6907 - 6910
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