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
[11]   METALLACYCLES Breaking the rules [J].
Beweries, Torsten ;
Rosenthal, Uwe .
NATURE CHEMISTRY, 2013, 5 (08) :649-650
[12]   Recent advances in the chemistry of heterometallacycles of group 4 metallocenes [J].
Beweries, Torsten ;
Haehnel, Martin ;
Rosenthal, Uwe .
CATALYSIS SCIENCE & TECHNOLOGY, 2013, 3 (01) :18-28
[13]   DIISOPROPOXYETHANE AND DI-TERT-BUTOXYETHYNE - STABLE ACETYLENE DIETHERS [J].
BOU, A ;
PERICAS, MA ;
SERRATOSA, F .
TETRAHEDRON, 1981, 37 (07) :1441-1449
[14]  
Brandenburg K, 2007, DIAMOND
[15]   THE TRIMETHYLPHOSPHINE ADDUCT OF THE ZIRCONOCENE BENZYNE COMPLEX - SYNTHESIS, REACTIONS, AND X-RAY CRYSTAL-STRUCTURE [J].
BUCHWALD, SL ;
WATSON, BT ;
HUFFMAN, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (23) :7411-7413
[16]   Interaction of carbon dioxide with acetylene complexes of titanocene Cp2Ti(RC2R) (R = Ph, SiMe3). Synthesis and structure of binuclear sigma-alkenylcarboxylate complexes of titanium (III) Cp2TiC(R)=C(R)COOTiCp2 and unexpected transformation of these complexes into titanafuranone metallacycles under the action of air oxygen [J].
Burlakov, VV ;
Yanovsky, AI ;
Struchkov, YT ;
Rosenthal, U ;
Spannenberg, A ;
Kempe, R ;
Ellert, OG ;
Shur, VB .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 542 (01) :105-112
[17]   THE FIRST TITANACYCLIC 5-MEMBERED CUMULENE - SYNTHESIS, STRUCTURE, AND REACTIVITY [J].
BURLAKOV, VV ;
OHFF, A ;
LEFEBER, C ;
TILLACK, A ;
BAUMANN, W ;
KEMPE, R ;
ROSENTHAL, U .
CHEMISCHE BERICHTE, 1995, 128 (10) :967-971
[18]   NOVEL ACETYLENE COMPLEXES OF TITANOCENE AND PERMETHYLTITANOCENE WITHOUT ADDITIONAL LIGANDS - SYNTHESIS, SPECRAL CHARACTERISTICS - AND X-RAY-DIFFRACTION STUDY [J].
BURLAKOV, VV ;
POLYAKOV, AV ;
YANOVSKY, AI ;
STRUCHKOV, YT ;
SHUR, VB ;
VOLPIN, ME ;
ROSENTHAL, U ;
GORLS, H .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1994, 476 (02) :197-206
[19]   Interaction of carbon dioxide with the bis(trimethylsilyl)acetylene complex of permethyltitanocene: Synthesis and structure of the binuclear carbonate complex of permethyltitanocene (Cp(2)(*)Ti)(2)CO3 [J].
Burlakov, VV ;
Dolgushin, FM ;
Yanovsky, AI ;
Struchkov, YT ;
Shur, VB ;
Rosenthal, U ;
Thewalt, U .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 522 (02) :241-247
[20]   REACTIONS OF INSITU GENERATED (ETA-2-PHENYLTRIMETHYLSILYLACETYLENE)ZIRCONOCENE [J].
ERKER, G ;
ZWETTLER, R .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 409 (1-2) :179-188
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