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.

引用

页码：5948 / 5957

页数：10

共 49 条

[1] ACETYLENE DERIVATIVES OF TITANOCENE [J].

ALT, HG ;

ENGELHARDT, HE ;

RAUSCH, MD ;

KOOL, LB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (12) :3717-3718

[2] ACETYLENE COMPLEXES OF TITANOCENE AS STARTING MATERIAL FOR 5-MEMBERED TITANACYCLES [J].

ALT, HG ;

HERRMANN, GS .

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 [J].

Altenburger, Kai ;

Semmler, Julia ;

Arndt, Perdita ;

Spannenberg, Anke ;

Meel, Matthias J. ;

Villinger, Alexander ;

Seidel, Wolfram W. ;

Rosenthal, Uwe .

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 [J].

Altenburger, Kai ;

Arndt, Perdita ;

Spannenberg, Anke ;

Baumann, Wolfgang ;

Rosenthal, Uwe .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2013, (18) :3200-3205

[5] Titanocene and Zirconocene Complexes with Diaminoacetylenes: Formation of Unusual Metallacycles and Fulvene Complexes [J].

Arias, Oscar ;

Petrov, Alex R. ;

Bannenberg, Thomas ;

Altenburger, Kai ;

Arndt, Perdita ;

Jones, Peter G. ;

Rosenthal, Uwe ;

Tamm, Matthias .

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 [J].

Arndt, P ;

Baumann, W ;

Spannenberg, A ;

Rosenthal, U ;

Burlakov, VV ;

Shur, VB .

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 [J].

Beweries, Torsten ;

Burlakov, Vladimir V. ;

Bach, Marc A. ;

Peitz, Stephan ;

Arndt, Perdita ;

Baumann, Wolfgang ;

Spannenberg, Anke ;

Rosenthal, Uwe ;

Pathak, Biswarup ;

Jemmis, Eluvathingal D. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (36) :6907-6910

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