| | 1 | Author
| Z. Naturforsch | Requires cookie* | | | Title
| Synthesis of Cationic Ruthenium Thioketene Complexes through Intramolecular 1,2-Elimination [1]  | | | | Abstract
| Halfsandwich thiocarboxylate complexes [CpRu(PR3)->(SC(0)CH2R')] ((P R 3)2 = (PPh3)2, Ph2PCH 2PPh2 (dppm), Ph2PC2H4PPh2 (dppe); R' = C6H 5, 4-C6H4Me, 4-C6H 4OMe, 4-C6H4C1) are obtained from the corresponding thiolate complexes [CpRu(PR3)2SH] and acyl chlorides. The structure of [CpRu(dppm)(SC(0)CHTPh)] was determined: monoclinic space group P2j/c (No. 14), a = 9.229(2), b = 16.680(3),"c = 21.447(5)Ä, ß = 90.751(12)°, Z = 4. Reaction of the thiocarboxylate complexes with the anhydrides of either trifluoro-acetic acid or trifluoromethanesulfonic acid gives thioketene complexes [CpRu(dppm) (?;2-S=C=CHR')]PF(s. H ie structure of [CpRu(dppm)0/2-S= C = C H Ph)]PF6 was deter mined: monoclinic space group P2,/c (No. 14), a -13.814(5), b -15.338(2), c = 17.057(7) Ä, ß = 93.74(2)°, Z = 4. | | | |
Reference
| (Z. Naturforsch. 52b, 117—124 [1997]; received July 25 1996) | | | |
Published
| 1997 | | | |
Keywords
| Ruthenium Complexes, Thiocarboxylate, Thioketene, Structure | | | |
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| default:Reihe_B/52/ZNB-1997-52b-0117.pdf | | | | Identifier
| ZNB-1997-52b-0117 | | | | Volume
| 52 | |
| 2 | Author
| WolfdieterA. Schenk, Thom As Stur | Requires cookie* | | | Title
| Elektronenreiche Ruthenium-Thiolat-Komplexe, Synthese und Reaktionen mit Elektrophilen Electron-Rich Ruthenium Thiolate Complexes, Synthesis and Reactions with Electrophiles | | | | Abstract
| Ruthenium thiolates [cpRu(PR'3)2(SR)] (PR ' 3 = PPh3, 1/2 dppe, 1/2 dppm, R = Me, C H 2Ph) are obtained from the corresponding chlorides and N aSR. PPh3 is readily exchanged for CO to give the chiral complexes [cpRu(PPh3)(CO)(SR)]. Alkylation with methyl tosylate yields the cations [cpRu(dppe)(SM eR)]+ and [cpRu(PPh3)(CO)(SM eR)]+, which were isolated as their PF6-salts. The neutral carbonyls add dimethyi acetylenedicarboxylate giving five-membered metallocycles. | | | |
Reference
| Z. Naturforsch. 45b, 1495—1498 (1990); eingegangen am 6. Juni 1990 | | | |
Published
| 1990 | | | |
Keywords
| Ruthenium Complexes, Thiolate Complexes, Cycloaddition | | | |
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| default:Reihe_B/45/ZNB-1990-45b-1495.pdf | | | | Identifier
| ZNB-1990-45b-1495 | | | | Volume
| 45 | |
| 5 | Author
| M. Onika Paulus, G.Erhard Thiele | Requires cookie* | | | Title
| Synthese und Kristallstruktur von Tris-//-chlorodichloro- tetrakis(dichlorsulfan)diruthenium(II, III), eines unsymmetrisch substituierten, gemischtvalenten Ruthenium(II, III)-Komplexes mit SCl2-Liganden Synthesis and Crystal Structure o f Tris-//-chlorodichlorotetrakis(disulfane)diruthenium(II, III) - an Unsymmetrically Substituted Mixed-Valence Ruthenium(II, III) Complex with SC12 Ligands | | | | Abstract
| Black crystals o f Ru2S4C113 have been obtained by reaction o f Ru with SC12 in closed quartz ampoules at 125 °C. The crystal structure o f the mixed-valence ruthenium(II, III) com pound (m onoclinic, a = 8.0262(15)Ä , b = 14.9612(33)Ä , c = 32.8876(55)Ä, ß = 97.03(1)°, space group P 2,/c, Z = 4) consists o f m olecules Ru2C15(SC12)4, in which the two Ru atom s are un symmetrically substituted by Cl and SC12 ligands. Octahedral units o f RuC15(SC12) and RuC13(SC12) 3 are Cl bridged to binuclear complexes C12(SC12)Ru(//-C1)3Ru(SC12)3. | | | |
Reference
| Z. Naturforsch. 47b, 253 (1992); eingegangen am 12. Juli/9. September 1991 | | | |
Published
| 1992 | | | |
Keywords
| Ruthenium Complex, M ixed-Valence, Sulphurdichloride, Crystal Structure | | | |
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| default:Reihe_B/47/ZNB-1992-47b-0253.pdf | | | | Identifier
| ZNB-1992-47b-0253 | | | | Volume
| 47 | |
| 6 | Author
| Z. Naturforsch | Requires cookie* | | | Title
| Ruthenium(II)-Komplexe mit dem neuen Liganden (Oxetanyl-2-methyl)diphenylphosphan | | | | Abstract
| R uthenium (II) C om plexes w ith the N ovel L igand (O xetanyl-2-m ethyl)diphenylphosphine E k k eh ard Lindner* und A ndrea M öckel The new ether-phosphine ligand (oxetanyl-2-m ethyl)diphenylphosphine (1) with strongly basic properties is obtained by reaction o f LiPPh2 with 2-chlorom ethyloxetane. Reaction o f 1 with Cl2Ru(PPh3)3 results in the formation o f the bis(chelate) com plex rra«5-Cl2R u (P " 0)2 (2). (P —O = z/'-P-coordinated; P " 0 = ^2-0,P -eoordinated). With CO only one R u -O bond is cleaved to give the monocarbonylruthenium(II) complex rra«^-Cl2R u (C 0) (P ~ 0)(P " 0) (3). 3 shows fluxional behaviour only at higher temperatures as demonstrated by 3IP {'H } N M R spectra. | | | |
Reference
| Z. Naturforsch. 47b, 693—6 (1992); eingegangen am 4. Dezember 1991 | | | |
Published
| 1992 | | | |
Keywords
| Oxetanyl-Phosphine, O-Basicity, Ruthenium Complexes, Fluxional Behaviour | | | |
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| default:Reihe_B/47/ZNB-1992-47b-0693.pdf | | | | Identifier
| ZNB-1992-47b-0693 | | | | Volume
| 47 | |
| 7 | Author
| Yoshimitsu Yamazaki, MidoriG. Oto1, ^. Yu-Ichi, Takenori Kageyama, Hiroaki Tomohiro, Okuno | Requires cookie* | | | Title
| Structure of Chloro(cyclopentadienone)- (cyclopentadienyl)ruthenium and its Cytotoxic Activity | | | | Abstract
| The structure of R u(cpO)(cp)C l com plex (3), which was precipitated from aqueous solutions of R u(cp)2Cl+PF6' (1), was determined by X-ray crystallographic analysis. The Ru-halogen bond distance was shorter and the dihedral angle be tween the rings was larger than the values re ported for the corresponding Br analogue, R u(cpO)(cp)Br (4). The com plex 3 (IC50 1 09 /iM) was more cytotoxic than 1 (IC50 163 //M) against mouse sarcoma S I80 cells, but less toxic than 4 (IC50 72 ,/M). | | | |
Reference
| Z. Naturforsch. 51b, 301 (1996); received September 21 1995 | | | |
Published
| 1996 | | | |
Keywords
| Ruthenium Complex, Cytotoxicity, X-Ray, Cyclic Voltammetry | | | |
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| default:Reihe_B/51/ZNB-1996-51b-0301_n.pdf | | | | Identifier
| ZNB-1996-51b-0301_n | | | | Volume
| 51 | |
| 8 | Author
| WolfdieterA. Schenk, Bernhard Steinmetz3, Michael Hagel3, Waldemar Adamb, ChantuR. Saha-Möllerb | Requires cookie* | | | Title
| Oxyfunctionalization of Allyl Thioether Ruthenium Complexes with Dimethyldioxirane [1] | | | | Abstract
| Allyl thioether complexes [CpRu(P-P)(SRR')lPF6 (P-P = Ph2PCH2PPh2 (dppm), PIitPCtH-iPPI^ (dppe), R = Me, Et, Ph, R' = 3-propenyl, 3-cyclohexenyl, 2-methyl-2-buten-4-yl) and [CpRu(chir)(SRR')]PF6 (chir = (S,S)-Ph2PCHMeCHMePPh2, R = Me, CH2Ph, R' = 2-methyl-2-buten-4-yl) are obtained from the corresponding thiolate complexes by reaction with the appropriate allyl bromide. Careful oxidation with dimethyldioxirane (DMD) gave the allyl sulfoxide complexes [CpRu(P-P)(MeS(0)CH2CH=CH2)]PF6 (P-P = dppm, dppe). Double ox idation to the corresponding sulfinylmethyl epoxide complexes can be readily achieved with an excess of DMD. Oxidation of the chir complexes proceeds with only moderate diastereoselectiv-ity. The structure of the (/?, R/S, S) diastereomer of [CpRu(dppm)(MeS(0)CH2CHCH2 0)]PF6 was determined: monoclinic space group P2]/c (No. 14), a = 11.21(2), b = 16.762(9), c = 18.45(4) A, ß = 94.4(1)°, Z = 4. For a representative example, the decomplexation of the sulfoxide-epoxide ligand by sodium iodide in acetone was demonstrated. | | | |
Reference
| Z. Naturforsch. 52b, 1359—1371 (1997); received September 9 1997 | | | |
Published
| 1997 | | | |
Keywords
| Ruthenium Complexes, Sulfoxide, Epoxide, Dimethyldioxirane, Structure | | | |
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| default:Reihe_B/52/ZNB-1997-52b-1359.pdf | | | | Identifier
| ZNB-1997-52b-1359 | | | | Volume
| 52 | |
| 9 | Author
| Bernhard Steinmetz, Michael Hagel, WolfdieterA. Schenk | Requires cookie* | | | Title
| Synthesis and Oxidation of Ruthenium Allyl Thioether Complexes Bearing Phosphite and Phosphonite Coligands [1] | | | | Abstract
| Halfsandwich ruthenium thiolate complexes bearing electron-withdrawing phosphite or phos phonite ligands were prepared from [CpRu(PPh3)2(SR)l (R = Ph, CH2Ph, Me) and triph-enylphosphite or (5,5')-bis(binaphthylphosphonito)ethane (bbpe), respectively. Reaction with l-bromo-3-methyl-2-butene in the presence of NH4PF6 gave the corresponding allylthioether complexes [CpRu(PR'3)2(S(R)CH2CH=CMe2)]PF6. Treatment with an excess of dimethyl dioxirane (DMD) transformed the triphenylphosphite derivatives into diastereomeric (oxiranyl-methyl)sulfoxide complexes with 18 -80% de. NMR monitoring of the reaction revealed that the oxidant attacks the sulfur atom and the C=C double bond with comparable rates. Sim ilar oxidation of the bbpe complexes gave mixtures of four diastereoisomers with ratios of (64 : 15 : 1 3 :8) and (51 : 24 : 15 : 10), respectively. | | | |
Reference
| Z. Naturforsch. 54b, 1265—1271 (1999); received July 2 1999 | | | |
Published
| 1999 | | | |
Keywords
| Ruthenium Complexes, Thioether, Sulfoxide, Epoxide, Dimethyldioxirane | | | |
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| default:Reihe_B/54/ZNB-1999-54b-1265.pdf | | | | Identifier
| ZNB-1999-54b-1265 | | | | Volume
| 54 | |
| 10 | Author
| WolfdieterA. Schenk, Nikolai Kuhnerta | Requires cookie* | | | Title
| Synthesis of Halfsandwich Ruthenium Complexes of Sulfinic Acid Esters [1] | | | | Abstract
| A series of halfsandwich ruthenium sulfinato complexes [CpRu(PR'3)2(SO:R)] (R = Me, CH 2Ph, C2H4Ph, Ph, 4 -CöH4Me; PR'3 = PM e3, 1/2 dppm) with various electronic and steric environments around the ruthenium centre, have been prepared by insertion of SO2 into a ruthenium carbon bond, by a direct ligand exchange reaction, or by oxidation of thiolato complexes with 3-chloroperoxybenzoic acid. The chiral complexes [CpRu(C0)(PPh3)(S0 2 R)] (R = Me, CH2Ph, Ph) were obtained similarly by oxidation of the corresponding thiolates with magnesium monoperoxyphthalate. Alkylation of the sulfinato complexes with oxonium salts [Rm 3 0 ]X (R" = Me, Et; X = B F 4 , PF6) gave ruthenium complexes of sulfinic acid esters, [C pRu(L)(L')(S(0)(0R ")R)]X in high yields and, for the chiral complexes, up to 82% de. The esters may be detached from the metal by ligand exchange with acetonitrile. Stronger nucleophiles such as I~ or SMe~ dealkylate the coordinated sulfinic acid esters. | | | |
Reference
| Z. Naturforsch. 55b, 527—535 (2000); received March 20 2000 | | | |
Published
| 2000 | | | |
Keywords
| Ruthenium Complexes, Sulfur Ligands, Diastereoselective Alkylations | | | |
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| default:Reihe_B/55/ZNB-2000-55b-0527.pdf | | | | Identifier
| ZNB-2000-55b-0527 | | | | Volume
| 55 | |
| 11 | Author
| Sylvia Ernst, Volker Kasack, Christian Bessenbacher, Wolfgang Kaim | Requires cookie* | | | Title
| Ein-und zweikernige Bis(2,2'-bipyridyI)ruthenium-Komplexe mit N,0-Mode!liganden für Dehydrogenase-Cofaktoren Mono-and Binuclear Bis(2,2'-bipyridine)ruthenium Complexes with N,0-Ligands Modelling Dehydrogenase Cofactors | | | | Abstract
| Coordination of substitutionally inert [Ru(bpy) 2 ] 2+ fragments (bpy: 2,2'-bipyridine) to the a-iminoketone chelate ligands pyrazine-2-dimethylcarboxamide (4) and 4,7-phenanthroline-5,6-dione (5) yields the complexes [(N,0-4)Ru(bpy) 2 ] 2 ®, [(0,0'-5 e)Ru(bpy) 2 ]® and {(N,0; N',0'-5)[Ru(bpy) 2 ] 2 } 4 ® which exhibit a rich electrochemistry. The distinctly different electronic structures of the complexes are evident from the ESR behaviour of paramagnetic intermediates: N.O-coordinated complexes have the unpaired electron residing in the ligand n system upon reduction, albeit with g<2 for the complex of 4 but with g>2 for the binuclear complex of 5. The paramagnetic 0,0'-coordinated mononuclear complex with 5 has its redox potentials shifted positively relative to that of the binuclear system. These results are particularly noteworthy because 4 and 5 can be regarded as model compounds for the flavin and methoxatin dehydrogenase cofactors. | | | |
Reference
| Z. Naturforsch. 42b, 425—430 (1987); eingegangen am 6. August 1986 | | | |
Published
| 1987 | | | |
Keywords
| Dehydrogenase Cofactors, Ruthenium Complexes, Oxidation States, ESR Spectra, a-Iminoketones | | | |
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| default:Reihe_B/42/ZNB-1987-42b-0425.pdf | | | | Identifier
| ZNB-1987-42b-0425 | | | | Volume
| 42 | |
| 12 | Author
| Max Herberhold, Wolfgang Bühlmeyer, Alfred Gieren, Thomas Hübner, J. Wu | Requires cookie* | | | Title
| | | | | Abstract
| Fragmentation of bis(rm-butyl) sulfur diimide, S(NBu') 2 (la), in the presence of Ru 3 (CO)i 2 leads to a yellow tetrahedrane-type complex Ru 2 (CO) 6 (Bu r NS) (3a) containing rer/-butyl sulfur imide as a six-electron ligand. According to the X-ray structure determination the N —S bond (1.716 Ä) is arranged perpendicular to the Ru —Ru axis (2.661 Ä). | | | |
Reference
| (Z. Naturforsch. 42b, 65—70 [1987]; eingegangen am 3. September 1986) | | | |
Published
| 1987 | | | |
Keywords
| Di(rm-butyl) Sulfur Diimide, tert-Butyl Sulfur Imide, Ruthenium Complex, Tetrahedrane Structures | | | |
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| default:Reihe_B/42/ZNB-1987-42b-0065.pdf | | | | Identifier
| ZNB-1987-42b-0065 | | | | Volume
| 42 | |
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