The fragment bis(acetylacetonato)ruthenium:: a meeting-point of coordination and organometallic chemistry

被引:24
作者
Bennett, MA [1 ]
Byrnes, MJ [1 ]
Kovácik, I [1 ]
机构
[1] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia
关键词
ruthenium; acetylacetonate; redox behaviour; alkene complexes; alkyne complexes; nucleophilic attack;
D O I
10.1016/j.jorganchem.2004.07.027
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reduction of [Ru(acac)(3)] with zinc in THF/H2O Provides a range of coordination and organometallic complexes containing Ru-II(acac)(2), whose chemistry is reviewed. Most of these compounds, including those containing alkenes, undergo reversible one-electron oxidation to their Ru-III(acac)(2) counterparts, and the alkene-ruthenium(III) cations have been detected by spectroclectro-chemistry. The cations derived from the chelate N-donor ligands o-CH2=CHC6H4NMe2 and o-PhC-=CC6H4NMe2 have been isolated and structurally characterized. Comparison of the metrical data establishes that, whereas the alkene is less firmly bound to Ru-III than to Ru-II, the alkyne is bound about as strongly to Ru-III as to Ru-II. Some uncharged nucleophiles (pyridine, diethylamine, PPh3) react with the cationic Ru-III complexes to give unusual, paramagnetic Ru-III-C sigma-bonded chelate complexes. (C) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:4463 / 4474
页数:12
相关论文
共 88 条
[1]   16- and 18-electron ruthenium(II) complexes of the neutral, potentially tridentate triamine ligand 2,6-[bis(dimethylamino)methyl]pyridine (NN′N) [J].
Abbenhuis, RATM ;
del Rio, I ;
Bergshoef, MM ;
Boersma, J ;
Veldman, N ;
Spek, AL ;
van Koten, G .
INORGANIC CHEMISTRY, 1998, 37 (08) :1749-1758
[2]   Synthesis and characterization of RuH2(H2)2(PiPr3)2 and related chemistry.: Evidence for a bis(dihydrogen) structure [J].
Abdur-Rashid, K ;
Gusev, DG ;
Lough, AJ ;
Morris, RH .
ORGANOMETALLICS, 2000, 19 (09) :1652-1660
[3]   Trans- and cis-water reactivities in d6 octahedral ruthenium(II) pentaaqua complexes:: Experimental and density functional theory studies [J].
Aebischer, N ;
Sidorenkova, E ;
Ravera, M ;
Laurenczy, G ;
Osella, D ;
Weber, J ;
Merbach, AE .
INORGANIC CHEMISTRY, 1997, 36 (26) :6009-6020
[4]   DINITROGEN COMPLEXES OF TRANSITION-METALS [J].
ALLEN, AD ;
HARRIS, RO ;
LOESCHER, BR ;
STEVENS, JR ;
WHITELEY, RN .
CHEMICAL REVIEWS, 1973, 73 (01) :11-20
[5]   Bridging and terminal half-sandwich ruthenium dinitrogen complexes and related derivatives:: A structural study [J].
Aneetha, H ;
Jiménez-Tenorio, M ;
Puerta, MC ;
Valerga, P ;
Mereiter, K .
ORGANOMETALLICS, 2002, 21 (04) :628-635
[6]  
[Anonymous], J CHEM SOC CHEM COMM
[7]   Structure and bonding in redox-active d(4), d(5) and d(6) alkyne complexes: Metal-alkyne moieties as electron sinks [J].
Bartlett, IM ;
Connelly, NG ;
Orpen, AG ;
Quayle, MJ ;
Rankin, JC .
CHEMICAL COMMUNICATIONS, 1996, (22) :2583-2584
[8]  
BENNET MA, 1995, COMPREHENSIVE ORGANO, V7, pCH9
[9]   Bis(acetylacetonato)bis(cyclooctene)ruthenium(II), cis-[Ru(acac)2(η2-C8H14)2]:: a synthetic precursor to trans- and cis-bis(acetylacetonato)ruthenium(II) complexes [J].
Bennett, MA ;
Chung, GL ;
Hockless, DCR ;
Neumann, H ;
Willis, AC .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1999, (19) :3451-3462
[10]   (Ethene)bis(acetylacetonato) complexes of divalent and trivalent ruthenium [J].
Bennett, MA ;
Byrnes, MJ ;
Willis, AC .
ORGANOMETALLICS, 2003, 22 (05) :1018-1028