Transition-metal complexes with sulfur ligands. 94. Synthesis and reactivity of nickel, palladium, and platinum complexes with the thiolate carbene ligand 'S2C'2-. X-ray structure determinations of [Ni(PMe3)('S2C')], [Ni(PPh3)('S2C')], [Ni('SC')2], [Pt(PMe3)('S2C')], and ('S2CO')2

1993 ◽  
Vol 32 (5) ◽  
pp. 538-546 ◽  
Author(s):  
Dieter Sellmann ◽  
Werner Prechtel ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Platinum Complexes ◽  
X Ray ◽  
Structure Determinations ◽  
Palladium And Platinum 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.

Transition Metal Complexes with Sulphur Ligands, Part 151 [1]. Ligand Enforced Configurations and Low-Spin States of [FeNS4] Cores in [FeII(L)('pyS4')] Complexes with σ and σ-π Ligands (L = N2H4, pyridine, PMe3, PnPr3; 'pyS4'2- = 2,6-bis(2-mercaptophenylthiomethyl)pyridine (2-))

2001 ◽  
Vol 56 (7) ◽  
pp. 581-588 ◽  
Author(s):  
Dieter Sellmann ◽  
Nicole Blum ◽  
Frank W. Heinemann
Keyword(s):  
Nmr Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Magnetic Measurements ◽  
Spin States ◽  
X Ray ◽  
Structure Determinations

The reactions of [Fe('pyS4')]2 with PMe3 , PnPr3 , N2H4 and pyridine afforded mononuclear [Fe(L)('pyS4')] complexes with L = PMe3 ( 1 ), PnPr3 (2 ), N2H4 (3) and pyridine (4). NMR spectroscopy, magnetic measurements and X-ray structure determinations revealed that all complexes exhibit frans-thiolate donors and low-spin FeII centres, irrespective of the σ-π or σ ligand character of L. In this regard, the properties of [Fe(L)('pyS4')] complexes strongly contrast with those of [Fe(L)('NHS4')] complexes ('NHS4'2- = 2 ,2 '-bis(2 -mercaptophenylthio)- diethylamine(2 -)) and indicate that the rigid py(CH2)2 entity of the 'pyS42- ligand is able to enforce trans configurations and low-spin states of complexes with [FeNS4 ] cores. In spite of their diamagnetism, confirming the absence of antibonding electrons, all complexes 1 to 4 are highly reactive and rapidly exchange their L ligands for CO to give [Fe(CO)('pyS4')]. Evidence was obtained that the oxidation of [Fe(N'-H4)('pyS4')] (3) yields the diazene complex [μ-N2 H2 {Fe('pyS4’)}2] (5).

Preparation, properties and structure of some intermediate nido- and arachno-monocarbaboranes

1981 ◽  
Vol 46 (10) ◽  
pp. 2345-2353 ◽  
Author(s):  
Karel Baše ◽  
Bohumil Štíbr ◽  
Jiří Dolanský ◽  
Josef Duben
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Nmr Spectra ◽  
Liquid Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
H Nmr ◽  
Starting Compound

The 6-N(CH3)3-6-CB9H11 carbaborane reacts with sodium in liquid ammonia with the formation of 6-CB9H12- which was used as a starting compound for preparing the 4-CB8H14, 9-L-6-CB9H13 (L = (CH3)2S, CH3CN and P(C6H5)3), 1-(η5-C5H5)-1,2-FeCB9H10-, and 2,3-(η5-C5H5)2-2,31-Co2CB9H10- carboranes. The 4-CB8H14 compound was dehydrogenated at 623 K to give 4-(7)-CB8H12 carborane. Base degradation of 6-N(CH3)3-6-CB9H11 in methanol resulted in the formation of 3,4-μ-N(CH3)3CH-B5H10. The structure of all compounds was proposed on the basis of their 11B and 1H NMR spectra and X-ray diffraction was used in the case of the transition metal complexes.

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