Oxo- and imido-alkoxide vanadium complexes as precatalysts for the guanylation of aromatic amines

被引：36

作者：

Romero-Fernandez, Javier ^{[1
]}

Carrillo-Hermosilla, Fernando ^{[1
]}

Antinolo, Antonio ^{[1
]}

Alonso-Moreno, Carlos ^{[1
]}

Rodriguez, Ana M. ^{[1
]}

Lopez-Solera, Isabel ^{[1
]}

Otero, Antonio ^{[1
]}

机构：

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

来源：

DALTON TRANSACTIONS | 2010年 / 39卷 / 28期

关键词：

OPENING METATHESIS POLYMERIZATION; RAY CRYSTAL-STRUCTURE; STRUCTURAL-CHARACTERIZATION; SUBSTITUTED GUANIDINES; OLEFIN POLYMERIZATION; MOLECULAR-STRUCTURE; DINUCLEAR NIOBIUM; KETIMIDE LIGANDS; METAL-COMPLEXES; N-H;

D O I：

10.1039/c0dt00064g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Vanadium oxo-alkoxide complexes [V(O)(Cl)(3-x)(OR)(x)] (x = 1, R = Me (1), Et (2), n-Pr (3); x = 2, R = Me (4), Et (5), n-Pr (6)) were obtained by a clean reaction between [V(O)Cl-3] and different excesses of ROSiMe3 silicon ethers. Imido complexes [V(NAr)(Cl)(3-x)(OR)(x)](2) (Ar = 2,6-i-Pr2C6H3; x = 1, R = Me (7), Et (8), n-Pr (9); x = 2, R = Me (10), Et (11), n-Pr (12)) were prepared in excellent yields by reaction of the oxo-alkoxide precursors and ArNCO. X-Ray crystal structure determinations for 7, 8 and 12 revealed dimeric structures with alkoxide bridges. Complexes 7-12 are precursor of highly active guanylation catalysts. The study of the catalytic reaction allow us to propose the non-participation of the imido moiety. This was confirmed when complexes 1-6 gave better catalysts under the same conditions. The simple and commercial [V(O)Cl-3] (16) can be proposed as the most effective catalyst in this series of vanadium complexes.

引用

页码：6419 / 6425

页数：7

共 52 条

[1] Well-Defined Regioselective Iminopyridine Rhodium Catalysts for Anti-Markovnikov Addition of Aromatic Primary Amines to 1-Octyne [J].

Alonso-Moreno, Carlos ;

Carrillo-Hermosilla, Fernando ;

Romero-Fernandez, Javier ;

Rodriguez, Ana M. ;

Otero, Antonio ;

Antinolo, Antonio .

ADVANCED SYNTHESIS & CATALYSIS, 2009, 351 (06) :881-890

[2] Catalytic hydroamination of alkynes and norbornene with neutral and cationic tantalum imido complexes [J].

Anderson, LL ;

Arnold, J ;

Bergman, RG .

ORGANIC LETTERS, 2004, 6 (15) :2519-2522

[3]

[Anonymous], 2004, SAINT V7 12A AR DET

[4] PREPARATION AND STRUCTURAL CHARACTERIZATION OF NEW ALKOXONIOBIUM(V) AND (ALKOXO) (AMIDO) (IMIDO)-NIOBIUM(V) COMPOUNDS - CRYSTAL-STRUCTURE OF [NBCL(MU-OME)[N(SIME3)2](NSIME3)]2 [J].

ANTINOLO, A ;

OTERO, A ;

URBANOS, F ;

GARCIABLANCO, S ;

MARTINEZCARRERA, S ;

SANZAPARICIO, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 350 (01) :25-34

[5] Synthesis and reactivity of new mono- and dinuclear niobium and tantalum imido complexes:: X-ray crystal structure of [Ta(η5-C5H4SiMe3)Cl2{=NC6Me4-4-(N(SiMe3)2)}] [J].

Antiñolo, A ;

Dorado, I ;

Fajardo, M ;

Garcés, A ;

Kubicki, MM ;

López-Mardomingo, C ;

Otero, A ;

Prashar, S .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2006, 691 (07) :1361-1368

[6] Synthesis and structural characterisation of new organo-diimido tantalum and niobium complexes [J].

Antiñolo, A ;

Dorado, I ;

Fajardo, M ;

Garcés, A ;

Kubicki, MM ;

López-Mardomingo, C ;

Otero, A .

DALTON TRANSACTIONS, 2003, (05) :910-917

[7] Carbodiimide metathesis catalyzed by vanadium oxo and imido complexes via imido transfer [J].

Birdwhistell, KR ;

Lanza, J ;

Pasos, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 584 (01) :200-205

[8] METAL ALKOXIDES AS PRECURSORS FOR ELECTRONIC AND CERAMIC MATERIALS [J].

BRADLEY, DC .

CHEMICAL REVIEWS, 1989, 89 (06) :1317-1322

[9]

*BRUK NON AXS, SHELXTL NT VERS 6 12

[10]

Bühl M, 1998, ANGEW CHEM INT EDIT, V37, P142

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