Transition metal complexes with sulfur ligands. XXXVIII. 18 and 19 electron iron(II) nitrosyl complexes with thiolato thioether ligands including nitrogen and oxygen donators in S5, OS4, NS4, S4 and S3 donator sets: synthesis and reactions of [Fe(NO)(‘S5’)]n+, [Fe(NO)(‘NHS4’)]n+ (n=0,1) and [Fe(NO)2(L)] and X-ray structure analysis of [Fe(NO)(‘NHS4’)]

1988 ◽  
Vol 154 (2) ◽  
pp. 157-167 ◽  
Author(s):  
Dieter Sellman ◽  
Herbert Kunstmann ◽  
Matthias Moll ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
X Ray ◽  
Nitrosyl Complexes

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.

Übergangsmetallkomplexe mit Schwefelliganden, LXX. / Transition Metal Complexes with Sulfur Ligands, LXX.

1991 ◽  
Vol 46 (11) ◽  
pp. 1449-1458 ◽  
Author(s):  
Dieter Sellmann ◽  
Bernd Seubert ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Molecular Structure ◽  
Nmr Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Structure Analysis ◽  
Transition Metal Complexes ◽  
Pentagonal Bipyramid ◽  
X Ray ◽  
Hydrogen Bonded

In order to study specific properties of transition metal sulfur complexes, reactions of [Mo(NO)2(′S4′)] (1) with nucleophiles were investigated. With sodiumborohydride or hydrazine, 1 yields the hydroxylaminyl complex [Mo(η2-NH2O)(NO)(′S4′)] (2). 2 crystallizes from DMF as 2 · DMF whose molecular structure was determined by X-ray structure analysis (P21/c, Z = 4, a = 1204.4(3), b = 1579.7(4), c = 1253.0(4) pm, β = 117.44(2)°, R = 0,056, Rw = 0,040). The Mo centre is coordinated by two trans thiolato S, two cis thioether S atoms, the co-ligand NO and side-on NH2O in a distorted pentagonal bipyramid; the DMF molecule is hydrogen bonded to the NH2O-ligand. NMR spectroscopy shows that in solution 2 exists in two configurational isomers differing in the orientation of the side-on NH2O with respect to the [Mo(NO)(′S4′)] core. The mechanism of the reduction of 1 is discussed in terms of a 2e--2H+-transfer.

Sign in / Sign up

Export Citation Format

Share Document