A high-yield method of synthesis of the acetato bridged endo-cyclopalladated dimer of benzyl-benzylidene-amine

被引：17

作者：

Albert, J ^{[1
]}

Bosque, R ^{[1
]}

Granell, J ^{[1
]}

Tavera, R ^{[1
]}

机构：

[1] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain

来源：

POLYHEDRON | 2001年 / 20卷 / 26-27期

关键词：

cyclometallation; palladium(II); benzyl-benzylidene-amine;

D O I：

10.1016/S0277-5387(01)00931-7

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reaction between benzyl-benzylidene-amine (1) and Pd(OAc)(2) in acetic acid has been reexamined in order to prepare its acetato bridged endo-cyclopalladated dimer, (mu -OAc)(2)[Pd(C6H4CH=NCH2C6H5)](2) (2), in high yield. The best results were obtained when 1 and Pd(OAc)(2) in a molar ratio of 2:1 were treated under reflux in acetic acid for 45 min. Under these conditions, 2 was isolated in 85% yield. Further, 2 reacted with LiCl, giving the corresponding chloro bridged cyclopalladated dimer (mu -Cl)(2)[Pd(C6H4CH=NCH2C6H5)](2) (3), which was isolated in 80% yield. In addition, 2 and 3 were converted into the mononuclear cyclopalladated compounds trans-N,P-[Pd(C6H4CH=NCH2C6H5)(OAc)(PPh3)] (4), trans -N,P-[Pd(C6H4CH=NCH2C6H5)-(Cl)(PPh3)] (5) and [Pd(C6H4CH=NCH2C6H5)(acac)] (6), which were characterised by elemental analysis, FAB(+), IR and NMR spectra. The reactivity of 4 and 5 towards solutions of PPh3 in CDCl3 showed that PPh3 was not a good enough sigma donor ligand to cleave the sigma (Pd-N) of 4 and 5. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：3225 / 3229

页数：5

共 30 条

[1] INSERTIONS OF DIPHENYLACETYLENE INTO CYCLOPALLADATED COMPOUNDS - CRYSTAL-STRUCTURE OF [PD((PHC=CPH)2C6H4CH2N=CH(2,6-C6H3CL2))BR] [J].

ALBERT, J ;

GRANELL, J ;

SALES, J ;

SOLANS, X .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1989, 379 (1-2) :177-185

[2] OXIDATIVE ADDITION OF ARYL-HALOGEN BONDS OF N-BENZYLIDENBENZYLAMINES TO PALLADIUM(0) COMPOUNDS [J].

ALBERT, J ;

BARRO, J ;

GRANELL, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1991, 408 (01) :115-123

[3] OPTICALLY-ACTIVE EXOCYCLIC CYCLOPALLADATED DERIVATIVES OF BENZYLIDENE-(R)-(1-PHENYLETHYL)AMINES - SYNTHESES AND X-RAY MOLECULAR-STRUCTURES OF [PD(2-((E)-(R)-CHMEN=CH-2',6'-CL2C6H3)C6H4)CL(PPH(3))] AND [PD(2-((Z)-(R)-CHMEN=CH-2',6'-F2C6H3)C6H4)I(PPH(3))] [J].

ALBERT, J ;

GRANELL, J ;

SALES, J ;

FONTBARDIA, M ;

SOLANS, X .

ORGANOMETALLICS, 1995, 14 (03) :1393-1404

[4] C- and O-metallation of N-benzylideneamines by palladium .2. Synthesis and X-ray crystal structure of [Pd(2{CH=N-(CH2)(2)-4'-(MeO)C6H4}-4,5-(MeO)(2)C6H2)Br(PPh(3))] [J].

Albert, J ;

Granell, J ;

Moragas, R ;

FontBardia, M ;

Solans, X .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1996, 522 (01) :59-67

[5] CYCLOMETALLATION REACTIONS OF N-(BENZYLIDENE)-BENZYLAMINES WITH PALLADIUM COMPOUNDS [J].

ALBERT, J ;

GRANELL, J ;

SALES, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1984, 273 (03) :393-399

[6]

Albert J, 1996, AN QUIM-INT, V92, P396

[7] CHIRAL CYCLOPALLADATED COMPOUNDS FOR ENANTIOMERIC PURITIES OF FUNCTIONALIZED PHOSPHINES BY MEANS OF MULTINUCLEAR NMR [J].

ALBERT, J ;

GRANELL, J ;

MULLER, G ;

SAINZ, D ;

FONTBARDIA, M ;

SOLANS, X .

TETRAHEDRON-ASYMMETRY, 1995, 6 (02) :325-328

[8] 5-MEMBERED AND 6-MEMBERED EXO-CYCLOPALLADATED COMPOUNDS OF N-BENZYLIDENEAMINES - SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [PDBR(PARA-MEOC6H3(CH2)2N=CH(2,6-CL2C6H3))(PPH3)] AND [PDBR(C6H4CH2N=CH(2,6-CL2C6H3))(PET3)2] [J].

ALBERT, J ;

GOMEZ, M ;

GRANELL, J ;

SALES, J ;

SOLANS, X .

ORGANOMETALLICS, 1990, 9 (05) :1405-1413

[9] CYCLOPALLADATION OF N-MESITYLBENZYLIDENEAMINES - AROMATIC VERSUS ALIPHATIC C-H ACTIVATION [J].

ALBERT, J ;

CEDER, RM ;

GOMEZ, M ;

GRANELL, J ;

SALES, J .

ORGANOMETALLICS, 1992, 11 (04) :1536-1541

[10] CYCLOMETALATION OF 3,5 DISUBSTITUTED N-BENZYLIDENEAMINES BY PALLADIUM(II) - SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [PD(3,5-F2C6H2CH=NC6H5)BR(PPH(3))(2)] [J].

ALBERT, J ;

GRANELL, J ;

MORAGAS, R ;

SALES, J ;

FONTBARDIA, M ;

SOLANS, X .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 494 (1-2) :95-103

← 1 2 3 →