Rolf D. Schmid

The substitution chemistry of RuCp* (temeda)Cl

SummaryHalide abstraction from RuCp*(tmeda)Cl (1,tmeda=Me2NCH2CH2NMe2) with NaBPh4 in CH2Cl2 leads to the formation of the sandwich complex RuCp*(η6-C6H5BPh3) (2). In the presence of CH3CN (1 equiv.) and CO, however, the cationic complexes [RuCp*(tmeda)(CH3CN)]+ (3) and [RuCp*(temeda)(CO)]+ (5) are obtained. In CH3CN,tmeda is also replaced giving [RuCp*(CH3CN)3]+ (4). Complex1 reacts readily with terminal acetylenes HC≡CR, the products depending on the nature ofR (Ph, SiMe3,n-Bu, COOEt). Thus, withR=Ph the ruthenacyclopentatriene complex RuCp*(σ,σ′-C4Ph2H2)Cl (6), withR=SiMe3 the cyclobutadiene complex Ru(Cp*)(σ4-C4H2(1,2-SiMe3)2)Cl (7), and withR=n-Bu and COOEt the binuclear complexes (Cp*)RuCl2(η2:η4-μ2-C4H2(1,3-R)2)Ru(Cp*) (8,9) are obtained. Furthermore, with diethyl maleate in the presence of 1 equiv. of LiCl,1 transforms into the new anionic complex Li[Ru(Cp*) (η2-C2H2(COOEt)2)Cl2] (10). X-ray structures of2,3,4,7, and10 are included.ZusammenfassungChloridabspaltung von RuCp*(tmeda)Cl (1,tmeda=Me2NCH2CH2NMe2) mittels NaBPh4 in CH2Cl2 führt zur Bildung des Halbsandwich-Komplexes RuCp*(η6-C6H5BPh3) (2), während in Gegenwart von CH3CN oder CO die beiden kationischen Verbindungen [RuCp*(tmeda)(CH3CN)]+ (3) und [RuCp*(tmeda)(CO)]+ (5) entstehen. In CH3CN als Lösungsmittel wird sogartmeda unter Bildung von [RuCp*(CH3CN)3]+ (4) verdrängt. Komplex1 reagiert sehr leicht mit terminalen Alkinen HC≡CR, wobei die Produkte stark von der Natur des SubstituentenR (Ph, SiMe3,n-Bu, COOEt) abhängen. Im Fall vonR=Ph entsteht der Ruthenacyclopentatrien-Komplex RuCp*(σσ′-C4Ph2H2)Cl (6), mitR=SiMe3 der Cyclobutadien-Komplex Ru(Cp*)(η4-C4H2(1,2-SiMe3)2)Cl (7), und im Fall vonR=n-Bu und COOEt bilden sich die binuklearen Komplexe (Cp*)RuCl2(η2:η4-μ2-C4H2(1,3-R)2)Ru(Cp*) (8,9). Überdies reagiert1 mit Maleinsäurediethylester in Gegenwart von LiCl zum neuen anionischen Komplex Li[Ru(Cp*) (η2-C2H2(COOEt)2)Cl2] (10). Von2,3,4,7 und10 wurden die Kristallstrukturen bestimmt.

Structure and bonding in a series of cyano complexes: RuCp(PPh3) 2CN, [RuCp(PPh3) 2(CNH)]CF3SO3, and H-bridged [Ru2(Cp) 2(PPh3) 4CNHNC]CF3SO3

Abstract The three title cyanoruthenium complexes have been characterized by means of X-ray diffraction analysis, IR and NMR solution spectroscopies, as well as extended Huckel molecular orbital calculations examining the properties of the cyanide fragment changing with complexation and with the co-ligands Cp and PPh3. Explanations are given for crystallographic results of the C-N bond shortening upon complexation, the supershort (2.573 A) bond length of N(H) ⋯ N in the bridged complex, as well as the Ru-C-N and C-N-H-N-C bendings. Although the crystallographically found asymmetry of coordinated Cp is not significant, the MO calculations suggest a distorted endocyclic bond-length pattern indicative of the relative importance of σ and π bonding in the metalcyclopentadienyl interactions.

Synthesis and X-ray structures of some mono- and binuclear ruthenium complexes with bisphosphine ligands

SummaryThe dinuclear complexes {RuCp*(μ-Cl)}2(μ-dppm) (1) and {RuCp*(μ-Cl)}2 (μ-dppe) (3) are obtained by reacting [RuCp*(μ3-Cl)]4 withdppm, anddppe, respectively.1 is readily oxidized with AgCF3SO3, instead of chloride abstraction, to afford the dinuclear complex [{RuCp*(μ-Cl)}2(μ-dppm)](SO3CF3)2 (2) with two metal centers connected by a single Ru-Ru bond. Under the same conditions,3 decomposes to several intractable materials. Similarly to1, RuCp* (dmpe)Cl reacts with AgCF3SO3 to afford the Ru(III) complex [RuCp*(dmpe)Cl](SO3CF3) (4) without no halide abstraction. The crystal structures of2,3, and4 are presented.ZusammenfassungDie Komplexe {RuCp*(μ-Cl)}2(μ-dppm) (1) und {RuCp*(μ-Cl2(μ-dppe) (3) wurden durch Umsetzung von [RuCp*(μ3-Cl)]4 mitdppm bzw.dppe dargestellt.1 wird durch AgCF3SO3 zum zweikernigen Komplex [{RuCp*(μ-Cl)}2(μ-dppm)](SO3CF3)2 (2) oxidiert, welcher eine Ru-Ru-Metallbindung aufweist. Unter den gleiche Reaktionsbedingungen zersetzt sich3 zu undefinierten Produkten. Analog zu1 reagiert RuCp* (dmpe)Cl mit AgCF3SO3 zum Ru(III)-Komplex [Ru(Cp*)(dmpe)Cl](SO3CF3) (4) wobei es zu keiner Chloridabspaltung kommt. Von2,3, und4 wurden die Kristallstrukturen bestimmt.

(Acetonitrile-N)(η4-2-methylbuta-1,3-diene)(η5-pentamethylcyclopentadienyl)ruthenium(II) trifluoromethanesulfonate

The title compound, [Ru{η 5 -C 5 (CH 3 ) 5 }{η 4 -CH 2 C(CH 3 )CHCH 2 }(CH 3 CN)](CF 3 SO 3 ) or [Ru(C 5 H 8 )(C 10 H 15 )(C 2 H 3 N)](CF 3 SO 3 ), contains a half-sandwich ruthenium complex with an exo-oriented π-bonded diene moiety inclined at an angle of 16.0 (2)° to the cyclopentadienyl ring. The coordination geometry of ruthenium can be described as a three-legged piano stool.

[Ru(η5-C5H5)(η4-C5H4O){As(CH3)3}]PF6 and [Ru(η5-C5H5)(η4-C5H4O){As(C6H5)3}]PF6

As part of studies on the syntheses and chemical reactions of ruthenium η 5 -cyclopentadienyl-η 4 -cyclopentadienone complexes, the crystal structures of the two title compounds, (η 4 -cyclopentadienone)(η 5 -cyclopentadienyl)(trimethylarsine)ruthenium hexafluorophosphate and (η 4 -cyclopentadienone)(η 5 -cyclopentadienyl)(triphenylarsine)ruthenium hexafluorophosphate, have been determined from single-crystal X-ray diffraction data. The metal complexes of the two title compounds are both of a bent-sandwich type, but differ somewhat in conformation. The cyclopentadienone moieties of both compounds are distinctly puckered at the C(2) and C(4) atoms, and the C=O groups are bent away from the Ru atom. Ru-C bond lengths vary from 2.137 (4) to 2.248 (4) A in (I), and from 2.159 (4) to 2.271 (4) A in (II). Ru-As bond lengths are 2.491 (1) A in (I) and 2.512 (1) A in (II)