Transition-metal complexes with sulfur ligands. 50. Sulfur bond cleavage in organosulfur ligands induced by PPh3/NO substitution reactions at [Ru(PPh3)2('L4')] centers. Synthesis and reactions of various (vinylthio)arenethiolate and related [Ru(NO)(Y)('L4')] (Y = PPh3, Cl) complexes. X-ray structure analysis of nitrosyl(triphenylphosphine)(1,2-benzenedithiolato)(1-(vinylthio)-2-benzenethiolato)ruthenium(III)

1990 ◽  
Vol 29 (10) ◽  
pp. 1822-1826 ◽  
Author(s):  
Dieter Sellmann ◽  
Isabella Barth ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Bond Cleavage ◽  
Substitution Reactions ◽  
X Ray ◽  
Sulfur Bond

Übergangsmetallkomplexe mit Schwefelliganden, LXXVI Redox- und Additionsreaktionen von Nickelkomplexen mehrzähniger Thioether-Thiolat-Liganden. Röntgenstrukturanalysen von (NMe4)2[Ni(′S2′)2] und [Ni(′S4 – C3′)(PMe3)] / Transition Metal Complexes with Sulfur Ligands, LXXVI Redox and Addition Reactions of Nickel Complexes with Multidentate Thioether-Thiolato Ligands. X-Ray Structure Determinations of (NMe4)2[Ni(′S2′)2] and [Ni(′S4–C3′)(PMe3)]

1991 ◽  
Vol 46 (12) ◽  
pp. 1601-1608 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Nickel Complexes ◽  
Addition Reactions ◽  
Coordination Geometry ◽  
X Ray ◽  
Square Planar ◽  
Structure Determinations

In order to elucidate specific properties of nickel sulfur complexes, redox and addition-elimination reactions of [Ni(′OS4')]2, [Ni(′NHS4')]2, [Ni(′S5')], [Ni('S4—C5')], and [Ni('S4—C3')] were investigated ('OS4′ 2' = 2,2'-bis(2-mercaptophenylthio)diethylether(2—), 'NHS4'2- = 2,2'-bis(2-mercaptophenylthio)diethylamine(2—), 'S5'2- = 2,2'-bis(2-mercaptophenylthio)diethylsulfide(2—), 'S4-C5'2- = 1,5-bis(2-mercaptophenylthio)pentane(2—), 'S4—C3'2- = 1,3-bis(2-mercaptophenylthio)propane(2—)).Cyclovoltammetry proves the complexes to be redox inactive between —1.4 and +0.8 V vs. NHE. Above +0.8 V the complexes are irreversibly oxidized, below —1,4 V desalkylation takes place and [Ni(′S,′)2]2- is formed. An X-ray structure analysis was carried out of (NMe4)2[Ni(′S2')2], which shows a planar anion with the Ni center in a nearly perfect square planar coordination. Distances and angles are practically identical to those in the [Ni(′S2')2-] monoanion.The complexes coordinate only phosphines as coligands, but thioether donors simultaneously decoordinate and, dependant of reaction temperature, mono- or trisphosphine complexes are formed. [Ni(′S4—C3')(PMe3)] was characterized by X-ray structure analysis and exhibits a square pyramidal coordination geometry.

Übergangsmetallkomplexe mit Schwefelliganden, CI*. Synthese und Struktur von N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4 / Transition Metal Complexes with Sulfur Ligands, Cl*. Synthesis and Structure of N2H5[Fe(N2H4)(S2C6H4)2] · 1,33N2H4

1994 ◽  
Vol 49 (5) ◽  
pp. 660-664 ◽  
Author(s):  
Dieter Sellmann ◽  
Helge Friedrich ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
High Spin ◽  
Transition Metal Complexes ◽  
X Ray ◽  
Labile N

Attempts to coordinate N2H4 to [Fe(S2C6H4)2] fragments lead to N2H5[Fe(N2H4)(S2C6H4)2], which crystallizes from MeOH/N2H4 solutions as the solvate [(N2H5){Fe(N2H4)(S2C6H4)2} · 1,33 N2H4]. 1, and has been characterized by X-ray structure analysis. 1 contains three discrete N2H5+ cations, four N2H4 solvate molecules and three independent [Fe(N2H4)(S2C6H4)2]- anions which are connected via an extended network of N-H ··· N and N-H ··· S bridges. N2H5[Fe(N2H4)(S2ChH4)2] and 1 contain high-spin Fe(III) centers and labile N2H4 ligands.

Bor-stabilisierte Ν,Ο-Carbene, II Röntgenstrukturanalyse von (trans-4,5-Dimethyloxazolidin-2-yliden)triphenylbor und N-Alkyliengen / Boron Stabilized Ν,Ο-Carbenes, II X-Ray Structure of (trans-4,5-Dimethyloxazolidin-2-ylidene)triphenylboron and N-Alkylations

1989 ◽  
Vol 44 (8) ◽  
pp. 917-922 ◽  
Author(s):  
Wolf Peter Fehlhammer ◽  
Hans Hoffmeister ◽  
Borislav Boyadjiev ◽  
Thomas Kolrep
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
X Ray ◽  
Mild Conditions

The X-ray structure analysis of (trans-4,5-dimethyloxazolidin-2-ylidene)triphenylboron reveals a stereochemistry of the carbene ligand which is almost identical with that in transition metal complexes. Deprotonation of triphenylboron stabilized oxazolidin-2-ylidenes with NaH leads to (oxazolin-2-ato)borates, which have been N-alkylated with [R3O+][BF4~] or RI under mild conditions.

Ubergangsmetallkomplexe mit Schwefelliganden, XXXIII*/ Transition Metal Complexes with Sulfur Ligands, XXXIII*

1987 ◽  
Vol 42 (10) ◽  
pp. 1298-1306 ◽  
Author(s):  
Dieter Sellmann ◽  
Gerhard Binker ◽  
Falk Knoch
Keyword(s):  
Electron Transfer ◽  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Model Reaction ◽  
X Ray ◽  
Hydride Complex ◽  
Elemental Analyses

Abstract In order to investigate the specific properties which are associated with metal sulfur cen­ters, the system Ru/S2C6H42- has been studied with respect to the synthesis of new com­plexes and their reactions as well as their structure. cis-(NBu4)(Ru(NO))(PMe4)(S2C6H4)2] reacts with an excess of PMe3 in boiling THF to give the paramagnetic (μeff = 0,96 B. M., 295 K) trans-(NBu4)(Ru(PMe4)2(S2C6H4)2) (I). A plausible intermediate in this reaction is the nitrido complex (NBu4)(Ru(N)(S2C6H4)2) (2) since 2 gives with one equivalent of PMe3 a very labile product which is probably (NBu4)(Ru(N)(PMe4)(S2C6H4)2) (3). but reacts with an excess of PMe3 even at 20 °C to give 1. The Ru(III) complex 1 is easily oxidized by O2 or PhN2BF4 to yield the diamagnetic Ru(IV) species trans-(Ru(PMe3)2(S2C6H4)2) (4). Remarkably, the transformation of 1 into 4 is achieved also by H+ ions, providing a model reaction for the coupled H+-electron transfer which has been discussed for substrate reactions at metal sulfur centers of enzymes. - The reaction of RuCl2(PMe3)4 with S2C6H42- yields [Ru(PMe3)4(S2C6H4)] (5) at 20 °C, even if an excess of S2C6H42- is applied. Upon heating in THF or EtOH, 5 looses one PMe3 ligand to give the 16e -complex [Ru(PMe4)4(S2C6H4)] (6) which rapidly coordinates CO to give [Ru(CO)(PMe4)4(S2C6H4)] (7); '1P NMR indicates a meridional coordination of PMe4 in 7, and consequently CO must be trans to S2C6H42-. 6 reacts also with LiAlH4 to yield a very sensitive hydride complex to which the tentative formula [Ru(H)2(PMe3)2(S2C6H4)] is assigned. All compounds were characterized by elemental analyses and spectroscopic means, the structures of I and 5 were determined by X-ray structure analysis.

Oxochlorierung von Übergangsmetall-Komplexen mit Thionylchlorid/Oxochlorination of Transition Metal Complexes with Thionyl Chloride

1998 ◽  
Vol 53 (2) ◽  
pp. 153-156 ◽  
Author(s):  
Carola Stoll ◽  
Ingo-Peter Lorenz ◽  
Heinrich Nöth ◽  
Thomas Seifert
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Thionyl Chloride ◽  
Vanadium Atom ◽  
X Ray

Abstract The reaction of the transition metal complexes CpV(CO)4 and [CpMo(CO)3]2 with thionyl chloride affords the oxodichlorides CpM(O)Cl2 (M = V, Mo) by oxidative decarbonylation. The X-ray structure analysis of CpV (O)Cl2 shows the pseudo tetrahedral “piano-stool” configuration for the central vanadium atom.

Reaktionen N-silylierter Endiamine, I Übergangsmetallkomplexe von 1,3-Diaza-2-sila-4-cyclopentenen / Reactions of N-Silated Endiamines, I Transition Metal Complexes of 1,3-Diaza-2-sila-4-cyclopentenes

1986 ◽  
Vol 41 (10) ◽  
pp. 1230-1238 ◽  
Author(s):  
Michael Zettlitzer ◽  
Heindirk tom Dieck ◽  
Lutz Stamp
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Structural Data ◽  
Spectroscopic Properties ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Poorly Soluble

Abstract1,3-Di̲aza-2-s̱ila-4-c̱yclopentenes 1 (DISC), which are electron-rich and easily oxidizable ole­ fins, form strongly coloured, but poorly soluble 1:1 adducts with cuprous halides, while silver trifluoromethylsulfonate oxidizes 1. Much more soluble and again strongly coloured complexes of stoichiometry LPdX2, (L)1.5PdX2 and L 2PdX2 are formed from 1 and palladium halides. The well-crystallizing adduct (PdCl2 · L)2 3a was chosen for an X-ray structure analysis (monoclinic, space group P2/c; a = 10.215(3), b = 14.681(3), c =23.642(5) Å , β = 101.31(2)°; Z = 8 ; R = 0.054), which revealed an almost planar DISC ligand in an oblique η2(C=C)-coordination relative to the π-plane. Structural data and rather peculiar spectroscopic properties encourage a comparison of 3a with complexes, in which an electron-rich olefin is split to give a bis(carbene) ligand system. The electronic reasons for the splitting of electron-rich olefins at d8 metals are discussed under symmetry considerations.

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