Reactions of Group 4 Metallocene Alkyne Complexes with Carbodiimides: Experimental and Theoretical Studies of the Structure and Bonding of Five-Membered Hetero-Metallacycloallenes

被引：63

作者：

Kaleta, Katharina ^{[2
]}

Ruhmann, Martin ^{[2
,3
]}

Theilmann, Oliver ^{[2
,3
]}

Beweries, Torsten ^{[2
]}

Roy, Subhendu ^{[1
]}

Arndt, Perdita ^{[2
]}

Villinger, Alexander ^{[3
]}

Jemmis, Eluvathingal D. ^{[1
,4
]}

Schulz, Axel ^{[2
,3
]}

Rosenthal, Uwe ^{[2
]}

机构：

[1] Indian Inst Sci, Dept Inorgan & Phys Chem, Bangalore 560012, Karnataka, India

[2] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany

[3] Univ Rostock, Inst Chem, Abt Anorgan Chem, D-18059 Rostock, Germany

[4] Indian Inst Sci Educ & Res Thiruvananthapuram, Thiruvananthapuram 695016, Kerala, India

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 14期

关键词：

EFFECTIVE CORE POTENTIALS; MOLECULAR CALCULATIONS; NICKEL(0) COMPLEXES; C BONDS; 1-ZIRCONACYCLOPENT-3-YNE; TITANOCENE; CARBON; AROMATICITY; ZIRCONOCENE; ACTIVATION;

D O I：

10.1021/ja111479j

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of the low-valent metallocene(II) sources Cp2Ti(eta(2)-Me3SiC2SiMe3) (7) and Cp2Zr(py)(eta(2)-Me3SiC2SiMe3) (11, Cp = eta(5)-cyclopentadienyl, py = pyridine) with carbodiimides RN=C=NR (R = Cy, i-Pr, p-Tol) leads to the formation of five membered hetero-metallacycloallenes Cp2M{Me3SiC=C=C[N(SiMe3)(R)]-N(R)} (9M-R) (M = Ti, R = i-Pr; M = Zr, R = Cy, i-Pr, p-Tol). Elimination of the alkyne (as the hitherto known reactivity of titanocene and zirconocene alkyne complexes would suggest) was not observed. The molecular structures of the obtained complexes were confirmed by X-ray studies. Moreover, the structure and bonding of the complexes 9Zr-Cy and 9Zr-p-Tol was investigated by DFT calculations.

引用

页码：5463 / 5473

页数：11

共 2 条

[1] Five-Membered Aromatic Heterocycles in Diels-Alder Cycloaddition Reactions: Theoretical Studies as a Complement of the Experimental Researches
Brasca, Romina
Della Rosa, Claudia
Kneeteman, Maria
Mancini, Pedro M. E.
LETTERS IN ORGANIC CHEMISTRY, 2011, 8 (02) : 82 - 87
[2] Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3
Kaleta, Katharina
Ruhmann, Martin
Theilmann, Oliver
Roy, Subhendu
Beweries, Torsten
Arndt, Perdita
Villinger, Alexander
Jemmis, Eluvathingal D.
Schulz, Axel
Rosenthal, Uwe
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (04) : 611 - 617

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