107944-69-4Relevant academic research and scientific papers
UEBERGANGSMETALL-FULVEN-KOMPLEXE XXVI. DUALE REAKTIVITAET DES 5-(C5H4CHO)Cr(CO)3>--ANIONS GEGENUEBER ELEKTROPHILEN: EIN NEUER SYNTHESEWEG ZU FUNKTIONELL SUBSTITUIERTEN CYCLOPENTADIENYL-KOMPLEXEN UND (FULVEN)Cr(CO)3-DERIVATEN. MOLEKUEL- UND KRISTALLSTRUKTUR VON ...
Edelmann, Frank,Toefke, Susanne,Behrens, Ulrich
, p. 87 - 108 (1986)
The reactivity of the (η5-formylcyclopentadienyl)M(CO)3 anions (M = Cr, Mo, W) towards electrophilic reagents has been studied.Electrophilic attack at the metal was found for molybdenum and tungsten, while the chromium derivative exhibits a novel type of dual reactivity.Oxidation of the anions leads to the dimeric formylcyclopentadienyl complexes 5-C5H4CHO)M(CO)3>2.Seven-coordinated compounds of the general type (η5-C5H4CHO)M(CO)3X (X = I, Sn(CH3)2Cl, Au(PPh3)) are obtained by treatment of the anions with I2, (CH3)2SnCl2 and (Ph3P)AuCl, respectively.The molecular structure of (η5-C5H4CHO)Cr(CO)3Au(PPh3) has been determined by X-ray diffraction.The molecule has a linear Cr-Au-P geometry and contains two semi-bridging carbonyl groups.Protonation of the 5-C5H4CHO)M(CO)3>- anions (M = Mo, W) via the unstable hydrides (η5-C5H4CHO)M(CO)3H yields the dimers 5-C5H4CHO)M(CO)3>2.The chromium derivative 5-C5H4CHO)Cr(CO)3>- is also accessible to electrophilic attack at the oxygen atom of the formyl substituent.In this way a series of new (η6-fulvene)Cr(CO)3 complexes has been prepared by treatment of 5-C5H4CHO)Cr(CO)3>- with various acyl halides RCOCl (R = CH3, t-C4H9, C6H5, p-ClC6H4, OC2H5).A binuclear η6-fulvene complex has been synthesized from the Cr anion and ClOC(CH2)6COCl.The complex (η6-fulvenylbenzoate)Cr(CO)3 was characterized by X-ray crystallography.The fulvene ligand is coordinated in the η6-fashion with a strong Cr-Cexo interaction (d(Cr-Cexo) 238.7(5) pm).
