Übergangsmetallkomplexe mit Schwefelliganden, LXXVIII. H+-, Lewis-Säure-Basen- und Ligandentransferreaktionen von Thioether-Thiolat-Nickelkomplexen. Röntgenstrukturanalysen von [Mo(O)(′OS4′ )] und [Mo(O)(′NhS4′)]/Transition Metal Complexes with Sulfur Ligands, LXXVIII. H+-, Lewis Acid-Base and Ligand Transfer Reactions of Thioether-Thiolato-Nickel Complexes. X-Ray Structure Determinations of [Mo(O)('OS4')] and [Mo(O)('NHS4')]

1992 ◽  
Vol 47 (1) ◽  
pp. 51-60 ◽  
Author(s):  
Dieter Sellmann ◽  
Stefan Fünfgelder ◽  
Falk Knoch
Keyword(s):  
Metal Complexes ◽  
Acid Methyl Ester ◽  
Transfer Reactions ◽  
Side Chain ◽  
X Ray ◽  
Thiolate Ligands ◽  
Convenient Synthesis ◽  
Structure Determinations ◽  
Ligand Transfer ◽  
Amino Propionic Acid

In order to elucidate specific properties of nickel sulfur complexes, reactions of recently synthesized [Ni('S5')], [Ni('OS4')]2, [Ni('NHS4')]2, [Ni('S4-C5')]2 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-)).Reactions with proton acids, CH3COCl and cyanide led to de-coordination of the sulfur ligands, thus providing a convenient synthesis of multidentate thioether-thiolate ligands.The reactions of these Ni complexes with metal salts or metal complexes led to ligand transfer from nickel to Pd(II), Mo(IV ) and Hg(II), [Pd('S4-C3')], [Hg('S5')], [Hg('S4-C3')]. [Hg('S4-C5')], [Mo(O)('S5')], [Mo(O)('NHS4')] and [Mo(O)('OS4')] were synthesized by this method. X-ray structure analysis proved that [Mo(O)('OS4')] and [Mo(O)('NHS4')] have a pseudooctahedral Mo coordination with cis-thiolate atoms and trans-ether or amine and oxogroup donors.Template alkylation of [Fe(CO)2(S2C6H4)2]2- by 3-(N, N-bis-(2-bromoethyl)-amino)-propionic acid methyl ester leads to a multidentate ligand that contains functional groups in the side chain.

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).

Convenient synthesis, separation, and x-ray crystal structure determinations of 1(e),3(e),5(e)-trimethylcycloborazane and 1(e),3(e),5(a)-trimethylcycloborazane

1986 ◽  
Vol 25 (19) ◽  
pp. 3346-3349 ◽  
Author(s):  
Chaitanya K. Narula ◽  
Jerzy F. Janik ◽  
Eileen N. Duesler ◽  
Robert T. Paine ◽  
Riley Schaeffer
Keyword(s):  
Crystal Structure ◽  
X Ray ◽  
Convenient Synthesis ◽  
Structure Determinations

Tris(trimethylphosphine)cobalt(0) Compounds Containing Azaolefinic Ligands — Syntheses and Structures of Benzo[c]cinnoline and Phenylisocyanate Complexes

1993 ◽  
Vol 48 (6) ◽  
pp. 785-793 ◽  
Author(s):  
Hans-Friedrich Klein ◽  
Michael Helwig ◽  
Michael Karnop ◽  
Herbert König ◽  
Birgit Hammerschmitt ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Carbon Monoxide ◽  
Cobalt Atom ◽  
Cyclic Dimer ◽  
X Ray ◽  
Convenient Synthesis ◽  
Mononuclear Cobalt ◽  
Structure Determinations

Mononuclear cobalt(0) complexes Co(η2-azaolefin)(PMe3)3 (azaolefin = benzo[c]cinnoline (1), p-dimethylamino-phenyl(phenyl)diazene (2), 1/2 diazobenzene (3), bis(p-tolyl)diazene (4), bis(p-fluorphenyl)diazene (5), bis(p-trifluoromethyl-phenyl)diazene (6), phenylisocyanate (7)) are obtained from Co(cyclo-C5H8)(PMe3)3 by substitution of the olefin. X-ray crystal structure determinations of 1 and 7 show tetrahedral arrangements of ligands around the cobalt atom. By reaction with carbon monoxide carbonyl(phosphine)cobalt(0) complexes are formed. 7 catalyses the cyclotrimerization of phenylisocyanate, while with CoCl(PMe3)3 as a catalyst the cyclic dimer of phenylisocyanate is selectively formed. A convenient synthesis for CoCl(PMe3)3 is described.

Cyclische Diazastannylene, XXX [1] Symmetrisch und asymmetrisch substituierte German- und Stannandiyle mit Amid-, Alkoholat- und Thiolat-Liganden, Teil I [2] / Cyclic Diazastannylenes, XXX [1] Symmetrically and Asymmetrically Substituted Germane- and Stannanediyls with Amide, Alcoholate and Thiolate Ligands, Part I [2]

1989 ◽  
Vol 44 (9) ◽  
pp. 1067-1081 ◽  
Author(s):  
M. Veith ◽  
P. Hobein ◽  
R. Rösler
Keyword(s):  
Chelate Ring ◽  
Membered Ring ◽  
Aluminium Atom ◽  
X Ray ◽  
Thiolate Ligands ◽  
Trigonal Bipyramidal ◽  
Tetrahedral Environment ◽  
Homologous Compounds ◽  
Structure Determinations ◽  
Tert Butylamine

Chelates of Ge(II) and Sn(II)Symmetrically and unsymmetrically substituted germane- and stannanediyls as well as chelated bis(amino)- or aminooxogermanium- and -tinmonohalides have been obtained from cyclic bis(amino)germane- and stannanediyls by treatment with tert-butylamine, tert-butanol and tert-butylmercaptane. The following compounds have been synthesized: GeX2 (X = OtBu (5), StBu (6)), Sn(StBu), (9), GeXCl (X = N(H)tBu (21), OtBu (22)), SnXCl (X = N(H)tBu (23), OtBu (24), StBu (25), OMe (28)) and Sn(OtBu)Br (27). In the series of the chelates Me2Si(NtBu)(NHtBu)GeCl (13), Me2Si(NtBu)(OtBu)SnX (X = Cl (18), OMe (19)) and the bischelate [Me2Si(NtBu)(OtBu)]2Sn (20) have been prepared. When 18 is allowed to react with aluminiumtrimethyl Me2Si(NtBu)(OtBu)AlClMe is formed, a compound with a center of chirality at the aluminium atom. X-ray structure determinations have been performed on single crystals of 6, 8, 9, 13, 22 and 24. 6, 8, 22 and 24 form molecular dimers with c.n. of 3 at the Ge or Sn atoms, resp. While the tBu-S ligands are syn with respect to the central Ge2S2 ring in 6 (symmetry approaching C2v), the tBu-O ligands are anti to the central Sn2O2 ring in 8 (symmetry Ci). 9 forms a coordination polymer with all Sn atoms in a Ψ-trigonal-bipyramidal and all S atoms in a Ψ-tetrahedral environment. The germanium atom in 13 is coordinated by a chlorine, a λ3- and a λ4-nitrogen atom, the two nitrogen atoms being connected by as dimethylsilyl group. The hydrogen and chlorine atom of 13 are found at the same side of the four-membered chelate ring. The two unsymmetrically substituted, homologous compounds Ge(O/tBu)Cl (22) and Sn(OtBu)Cl (24) are found to form dimers via O→Ge resp. O→Sn bonds. While the chlorine atoms in 22 are syn with respect to the four-membered ring, they are anti in the case of molecule 24.

Cobalt(II) and cadmium(II) metal complexes of a 2-aminobenzimidazole-thiazine derivative ligand. Synthesis, characterization and X-ray structure determinations

Polyhedron ◽  
2005 ◽  
Vol 24 (13) ◽  
pp. 1764-1772 ◽  
Author(s):  
F.J. Barros-García ◽  
A. Bernalte-García ◽  
F. Luna-Giles ◽  
M.A. Maldonado-Rogado ◽  
E. Viñuelas-Zahínos
Keyword(s):  
Metal Complexes ◽  
X Ray ◽  
Structure Determinations ◽  
Ligand Synthesis

Synthesis and Structure of Bis[di(methylcyclopentadienyl)chloro-titanium]trisulfide [(Cp′2ClTi)2S3] - a Reagent for Trisulfide Ligand Transfer Reactions [1]

1997 ◽  
Vol 52 (1) ◽  
pp. 79-82 ◽  
Author(s):  
Ralf Steudel ◽  
Monika Kustos ◽  
Andreas Prenzel
Keyword(s):  
Structure Analysis ◽  
Nmr Spectra ◽  
Transfer Reactions ◽  
X Ray ◽  
Ligand Transfer ◽  
Titanium Trisulfide ◽  
C Nmr

The dinuclear metallacycle of [Cp′2Ti(μ-S2)2TiCp′2.] reacts with phosgene or thiophosgene to give [(Cp′2CITi)2S3] which has been characterized by 1H and 13C NMR spectra as well as by an X-ray structure analysis. The trisulfido complex contains a helical TiSSSTi unit and may serve as an S3 transfer reagent in reactions with SCl-functional compounds

Sign in / Sign up

Export Citation Format

Share Document