TRIPLE-DECKER COMPLEXES .9. TRIPLE-DECKER COMPLEXES WITH BRIDGING CYCLOPENTADIENYL LIGANDS AND NOVEL CYCLOPENTADIENYL TRANSFER-REACTIONS

被引：74
作者：
HERBERICH, GE [1 ]
ENGLERT, U [1 ]
MARKEN, F [1 ]
HOFMANN, P [1 ]
机构：
[1] TECH UNIV MUNICH,INST ANORGAN CHEM,D-85747 GARCHING,GERMANY
来源：
ORGANOMETALLICS | 1993年 / 12卷 / 10期
关键词：
D O I：
10.1021/om00034a041
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The pentamethylmetallocenes CpMCp* (M = Ru, Fe) react with [Cp*Ru(OMe)]2/CF3SO3H in ether to give triple-decker salts [Cp*M(mu-Cp)RuCp*]CF3SO3 (4.CF3SO3, M = Ru; 5.CF3SO3, M = Fe) with an unsubstituted Cp as the bridging ligand. The structure of 4.CF3SO3.THF shows average metal-ring distances of 177.6(1) pm for the outer Cp* ligands and of 185.5(1) pm for the bridging Cp ring. The metalloelectrophiles [LM(solv)3]2+, generated from the dichlorides [(C6Me6)RuCl2]2, (Cp*RhCl2)2, (Cp*IrCl2)2, [(C4Me4)PtCl2]2, and AgCF3SO3 in MeNO2-d3, react with CpRuCp* at room temperature to undergo novel cyclopentadienyl transfer reactions, thus forming the cations [LMCp]+ besides 4+. With CpFeCp* labile triple-decker dications [LMCpFeCp*]2+ are formed in MeNO2-d3 at 0-degrees-C while at higher temperature cyclopentadienyl transfer (for Ru, Ir) or alternatively redox reactions (for Rh, Pt) are observed. [(C6Me5)Ru(acetone)3](CF3SO3)2 reacts with Fe(C5H4CHO)2 in acetone to give, after crystallization from CHCl3, [(C6Me6)Ru(C5H4CHO)]CF3SO3.CHCl3 (70%). Extended Huckel MO calculations for CpFeCp* reveal weaker bonds to the Cp side and an asymmetric charge distribution with total net charges of -0.093 for the Cp and +0.104 for the Cp* fragments. This suggests that the observed regiochemistry of the stacking and ring ligand transfer reactions of 1 and 2 is primarily of electronic origin.
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页码：4039 / 4045
页数：7
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