Structure and chemistry of the complex tetrakis(.eta.5-pentamethylcyclopentadienyl)tetrakis(.mu.3-chloro)tetraruthenium(II): a useful precursor to (pentamethylcyclopentadienyl)ruthenium(0), -(II), and -(IV) complexes

Abstract

A single-crystal X-ray structural analysis of the complex [Cp*R~(p~-Cl)1~ (1, Cp* = q5-C5(CH3),) has been performed (triclinic, P1 (No. 2); a = 11.281 (5); b = 11.354 (4); c = 18.846 (5) A; a = 82.20 (2)O, j3 = 82.03 (3)O, y = 65.45 (4)O; V = 2166.3 A3, 2 = 2). The complex contains a distorted cubic array of ruthenium and chlorine atoms. The complex 1 is a useful precursor to Ru(O), Ru(II), and Ru(1V) pentamethylcyclopentadienyl complexes. Reaction of 1 with donor ligands yields Cp*RuL2Cl complexes (L = CO, P(CHd3). With dienes, 1 yields the complexes Cp*Ru(q4-diene)C1 () which in turn can be reduced with lithium to yield the corresponding anionic diene complexes Cp*Ru(q4-diene)-Li+.DME (DME = 1,2-dimethoxyethane). The complex [Cp*Ru(p3-I)], has also been prepared and reacts with l,&butadiene to yield Cp*Ru(q4-scis-1,3-butadiene)I, which has been structurally characterized by a single-crystal X-ray analysis (monoclinic b, P2,/c (No. 14); a = 7.177 (2); b = 14.362 (3); c = 13.788 (2) A; 0 = 93.39 (1)O; V = 1418.7 A3, 2 = 4).Reaction of 1 with ethylene yields the complex [Cp*Ru(4-C2H4)Cl],, which can be converted to the complex C~* R U (~~-C~H , )~L~.With allyl chloride, 1 yields the oxidative addition product Cp*Ru(03-C3H5)Cl,.

Ruthenium‐Catalyzed O‐Allylation of Phenols from Allylic Chlorides via Cationic [Cp*(η3‐allyl)(MeCN)RuX][PF6] Complexes

“…The synthesis of [Cp*(MeCN) 3 Ru][PF 6 ] (1) was adapted from previous work as detailed below. [4,21] [Cp*(MeCN) 3 Ru][PF 6 ] (1) A mixture consisting of [Cp*RuCl] 4 (12.4 g, 11.4 mmol), KPF 6 (8.50 g, 46.2 mmol), and acetonitrile (100 mL) was stirred overnight and then heated to reflux to be filtered. The hot dark-orange filtrate deposited orange crystals of 1 upon cooling to 0 8C.…”

Ruthenium-Catalyzed Dimerization of 1,1-Diphenylpropargyl Alcohol to a Hydroxybenzocyclobutene and Related Reactions

“…Formic acid was dried over boric oxide and distilled. The ruthenium complexes [Cp*RuCl(diene)] [31] and [Cp*RuH(cod)] [32] were prepared according to the literature. 1 H (399.8 MHz) and 13 C{ 1 H} (100.53 MHz) NMR spectra were obtained on a JEOL JNM-ECX-400 spectrometer (JEOL Ltd., Tokyo, Japan).…”

NewP,N-Chelate Ligands Based on Pyridyl-Substituted Phosphaferrocenes

“…[1] [5] If grated 31 P-NMR spectra. Interestingly, the reactions with the reactants are mixed in a metal-to-ligand ratio of 1:1 in CO lead to almost complete epimerization at the Ru centre THF the quantitative formation of the anticipated chelate (dr < 60:40), whereas the additions of PPh 3 proceed with complexes [Cp*RuCl·3] (9) and [Cp*RuCl·6] (10) is ob-diastereoselectivities of dr ϭ 92:8 and 86:14; thus, the served within a few moments by NMR spectroscopy.…”

“…This π for other catalytic reactions for which the ligand type deacidity has another consequence involving the PdϪC bond scribed here might be better suited. lenghts: the distances PdϪC30 [2.12 (1) [11] [Cp*RuCl] 4 , [5] was observed in complexes with ferrocene-derived P,N li-[(C 3 H 5 )PdCl] 2 [12] and di-µ-chlorobis(1,3-diphenyl-π-allyl)dipalladium [13] were prepared as described in the literature.…”

“…The homologous pyridylethyl ligand 6 with a backbone ex-vated alumina and exhibit resonances in the 31 P-NMR spectra in the expected range [δ ϭ Ϫ77.1 (3) and Ϫ80.2 (6)]. tended by one CH 2 unit is obtained in an analogous reaction sequence when 2-(lithiomethyl)pyridine Ϫ prepared Recently, Mathey and coworkers reported the synthesis of the 2-(2Ј-pyridyl)phosphaferrocene ligand 8 by combining from 2-methylpyridine by deprotonation with nBuLi Ϫ is employed as the nucleophilic reagent.the [1,5]-sigmatropic rearrangement of the P-pyridyl-substituted phosphole 7 with the complexation reaction with If the work-up procedure of the preliminarily formed alcohol 4 (de 60%) is carried out under slightly acidic con-[CpFe(CO) 2 ] 2 in a one-pot procedure. [3] Eur.…”