Dendrimers containing two metallic layers. Chloride migration from peripheral gold, palladium, or rhodium metals to internal ruthenium atoms

被引:19
作者
Angurell, I [1 ]
Rossell, O [1 ]
Seco, M [1 ]
Ruiz, E [1 ]
机构
[1] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain
关键词
D O I
10.1021/om0504699
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
An efficient strategy for the synthesis of carbosilane dendrimers containing double metallic layers has been developed. The method consists of the attachment of the Ru(p-cymene)Cl-2 unit to the branches of a phosphino-terminated dendrimer, followed by abstraction with AgOTf of the chloride ligands from the ruthenium and selective incorporation, through the nitrogen pyridine atom, of the bifunctional 4-pyPPh(2) molecule. Finally, metalation of the resulting species with the complexes [(tht)AuCl], [PdCl(eta(3)-2-MeC3H4)](2), and [RhCl(cod)](2) renders the targeted Ru/Au, Ru/Pd, and Ru/Rh dendrimers. An unexpected migration of the chloride ligand bonded to the peripheral metals to the internal ruthenium atoms was observed and discussed in terms of the results obtained from density functional calculations. In the case of the Ru/Au dendrimers, the different abilities for the ligand transfer process shown by the dendrimers in comparison with a mononuclear Ru/Au model compound are explained in terms of dendritic effects.
引用
收藏
页码:6365 / 6373
页数:9
相关论文
共 46 条
[1]   Introduction of the cluster fragment Ru3(CO)11 at the periphery of phosphine dendrimers catalyzed by the electron-reservoir complex [FeICp(C6Me6)] [J].
Alonso, E ;
Astruc, D .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (13) :3222-3223
[2]   ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].
ANDRAE, D ;
HAUSSERMANN, U ;
DOLG, M ;
STOLL, H ;
PREUSS, H .
THEORETICA CHIMICA ACTA, 1990, 77 (02) :123-141
[3]   Single and double metallic layer-containing ruthenium dendrimers. Synthesis and catalytic properties [J].
Angurell, I ;
Muller, G ;
Rocamora, M ;
Rossell, O ;
Seco, M .
DALTON TRANSACTIONS, 2004, (16) :2450-2457
[4]   Synthesis and catalytic properties of neutral and cationic rhodium- and iridium-containing carbosilane dendrimers [J].
Angurell, I ;
Muller, G ;
Rocamora, M ;
Rossell, O ;
Seco, M .
DALTON TRANSACTIONS, 2003, (06) :1194-1200
[5]  
[Anonymous], ADV DENDR MACROMOL
[6]  
[Anonymous], INORG SYNTH
[7]   Synthesis of carbosilane dendrimers containing peripheral (cyclopentadienyl)(aryloxy)titanium(IV) units [J].
Arévalo, S ;
de Jesús, E ;
de la Mata, FJ ;
Flores, JC ;
Gómez, R .
ORGANOMETALLICS, 2001, 20 (12) :2583-2592
[8]   Dendritic catalysts and dendrimers in catalysis [J].
Astruc, D ;
Chardac, F .
CHEMICAL REVIEWS, 2001, 101 (09) :2991-3023
[9]   Dendrimers based on photoactive metal complexes. Recent advances [J].
Balzani, V ;
Ceroni, P ;
Juris, A ;
Venturi, M ;
Campagna, S ;
Puntoriero, F ;
Serroni, S .
COORDINATION CHEMISTRY REVIEWS, 2001, 219 :545-572
[10]   Dendrimers as luminescent hosts for metal cations and organic molecules [J].
Balzani, V ;
Vögtle, F .
COMPTES RENDUS CHIMIE, 2003, 6 (8-10) :867-872