Molecular Structure of a Hydridoniobocene Complex [Nb(η5-C5H4SiMe3)2(H)3] and Its Use as Catalyst for the Ring-Opening Polymerization of Cyclic Esters

被引：12

作者：

Alonso-Moreno, Carlos ^{[2
]}

Antinolo, Antonio ^{[1
]}

Garcia-Martinez, Joaquin C. ^{[2
]}

Garcia-Yuste, Santiago ^{[1
]}

Lopez-Solera, Isabel ^{[1
]}

Otero, Antonio ^{[1
]}

Perez-Flores, Juan C. ^{[1
]}

Tercero-Morales, Maria T. ^{[1
]}

机构：

[1] Univ Castilla La Mancha, Fac Ciencias Quim, Dept Quim Inorgan Organ & Bioquim, E-13071 Ciudad Real, Spain

[2] Univ Castilla La Mancha, Fac Farm, Dept Quim Inorgan Organ & Bioquim, Albacete 02071, Spain

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2012年 / 07期

关键词：

Metallocenes; Ring-opening polymerization; Hydride ligands; Niobium; Lactones; SINGLE-SITE CATALYSTS; SPECTROSCOPIC PROPERTIES; ZINC; TRIHYDRIDE; REACTIVITY; CHEMISTRY; NIOBIUM; LACTIDE;

D O I：

10.1002/ejic.201101263

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The second polyhydridoniobocene complex that was characterized by X-ray diffraction is reported. On the basis of H-H distances and H-Nb-H angles, [Nb(eta(5)-C5H4SiMe3)(2)(H)(3)] (1) is classified as a "compressed hydride". Compound 1 acts as an efficient single-component initiator for the ring-opening polymerization of epsilon-caprolactone and delta-valerolactone. epsilon-Caprolactone and delta-valerolactone are both polymerized within a few hours to yield high-to-medium-molecular-weight polymers with medium to broad polydispersities. Polymer end-group analysis showed that the polymerization proceeds through a coordination-insertion mechanism based on the cleavage of the ring between the oxygen atom and the acyl carbon atom.

引用

页码：1139 / 1144

页数：6

共 44 条

[31]

OTERO A, 2009, ANGEW CHEM, V121, P2210

[32] Neutral and Cationic Aluminum Complexes Supported by Acetamidate and Thioacetamidate Heteroscorpionate Ligands as Initiators for Ring-Opening Polymerization of Cyclic Esters [J].

Otero, Antonio ;

Lara-Sanchez, Agustin ;

Fernandez-Baeza, Juan ;

Alonso-Moreno, Carlos ;

Castro-Osma, Jose A. ;

Marquez-Segovia, I. ;

Sanchez-Barba, Luis F. ;

Rodríguez, Ana M. ;

Garcia-Martinez, Joaquin C. .

ORGANOMETALLICS, 2011, 30 (06) :1507-1522

[33] Ring-Opening Polymerization of Cyclic Esters by an Enantiopure Heteroscorpionate Rare Earth Initiator [J].

Otero, Antonio ;

Fernandez-Baeza, Juan ;

Lara-Sanchez, Agustin ;

Alonso-Moreno, Carlos ;

Marquez-Segovia, Isabel ;

Sanchez-Barba, Luis F. ;

Rodriguez, Ana M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (12) :2176-2179

[34]

Peruzzini M., 2001, RECENT ADV HYDRIDE C, P4

[35]

Shalaby S. W., 2003, ADV POLYM MAT

[36]

Sheldrick G. M., 1994, SHELX93 PROGRAM DETE

[37] PHASE ANNEALING IN SHELX-90 - DIRECT METHODS FOR LARGER STRUCTURES [J].

SHELDRICK, GM .

ACTA CRYSTALLOGRAPHICA SECTION A, 1990, 46 :467-473

[38] Aspects of dihydrogen coordination chemistry relevant to reactivity in aqueous solution [J].

Szymczak, Nathaniel K. ;

Tyler, David R. .

COORDINATION CHEMISTRY REVIEWS, 2008, 252 (1-2) :212-230

[39] Stereocontrolled ring-opening polymerization of cyclic esters: synthesis of new polyester microstructures [J].

Thomas, Christophe M. .

CHEMICAL SOCIETY REVIEWS, 2010, 39 (01) :165-173

[40] Consequences of Polylactide Stereochemistry on the Properties of Polylactide-Polymenthide-Polylactide Thermoplastic Elastomers [J].

Wanamaker, Carolyn L. ;

Bluemle, Michael J. ;

Pitet, Louis M. ;

O'Leary, Leslie E. ;

Tolman, William B. ;

Hillmyer, Marc A. .

BIOMACROMOLECULES, 2009, 10 (10) :2904-2911

← 1 2 3 4 5 →