Synthesis, structural characterization, and reactivity of late transition-metal complexes bearing linked cyclopentadienyl–carboranyl ligands

2012 ◽  
Vol 90 (1) ◽  
pp. 108-117 ◽  
Author(s):  
Dongmei Liu ◽  
Zaozao Qiu ◽  
Hoi-Shan Chan ◽  
Zuowei Xie
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Structural Characterization ◽  
Molecular Structures ◽  
Spectroscopic Techniques ◽  
Late Transition Metal ◽  
X Ray ◽  
Elemental Analyses ◽  
Late Transition

Late transition-metal complexes bearing linked cyclopentadienyl/indenyl–carboranyl ligands were synthesized and their reactivities were examined. Reaction of Li2[Me2C(L)(C2B10H10)] (L = C5H4, C9H6, Me2NCH2CH2C5H3) with MCl2(PPh3)2 in Et2O afforded [η5:σ-Me2C(C5H4)(C2B10H10)]M(PPh3) (M = Co (4), Ni (5)), [η5:σ-Me2C(C9H6)(C2B10H10)]M(PPh3) (M = Co (6), Ni (7)), and [η5:σ-Me2C(Me2NCH2CH2C5H3)(C2B10H10)]Ni(PPh3) (8). Treatment of 4 or 5 with 2,6-dimethylphenylisocyanide, N-heterocyclic carbene (NHC), PCy3, or 1,2-bis(diphenylphosphino)ethane (dppe) gave the corresponding PPh3 displacement complexes [η5:σ-Me2C(C5H4)(C2B10H10)]M(2,6-Me2C6H3NC) (M = Co (9), Ni (10)), [η5:σ-Me2C(C5H4)(C2B10H10)]M[1,3-(2,6-i-Pr2C6H3)2C3N2H2] (M = Co (11), Ni (12)), [η5:σ-Me2C(C5H4)(C2B10H10)]Ni(PCy3) (13), or {[η5:σ-Me2C(C5H4)(C2B10H10)]Co}2(dppe) (14), respectively. These complexes were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 4–14 were further confirmed by single-crystal X-ray analyses.

Bis-2-thienyldiethylaminophosphane as a Ligand in Late Transition Metal Complexes and its Transformation to Bis-2-thienylphosphane

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1429-1440
Author(s):  
Markus Granitzka ◽  
Peter Stollberg ◽  
Dietmar Stalke
Keyword(s):  
Nmr Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Metal Salts ◽  
Inert Gas ◽  
Late Transition Metal ◽  
X Ray ◽  
Transition Metal Salts ◽  
Late Transition

Abstract Bis-2-thienyldiethylaminophosphane (C4H3S)2PNEt2 (1) is introduced as a ligand for late transition metal complexes ([(H3C4S)2PNEt2]nMXmLp), with M = Ni(II), Au(I), Cu(I), Pd(II), Ir(I), X = Cl, Br and L = NCMe, COD, (2-7). Reactions of 1 with the late transition metal salts NiCl2·dme, (Me2S)AuCl, CuCl, PdCl2(PhCN)2, and [Ir(COD)Cl]2 yield the complexes [{(H3C4S)2PNEt2}2 · NiCl2] (2), [(H3C4S)2PNEt2 · AuCl] (3) [(H3C4S)2PNEt2·CuCl(CH3CN)]2 (4), [{(H3C4S)2PNEt2}2 · PdCl2] (5), [{(H3C4S)2PNEt2}2·PdCl2]2 (6), and [(H3C4S)2PNEt2·IrCl(COD)] (7). In addition, the transformation of 1 to the valuable chlorine-substituted starting material (H3C4S)2PCl (8) and the related conversion of 8 to the secondary phosphane (H3C4S)2PH (9) is reported. The complexes 2-7 are stable under inert gas conditions and were characterized by single-crystal X-ray studies, NMR spectroscopy, and elemental analysis.

Hydrosilylation as an efficient tool for polymer synthesis and modification with methacrylates

RSC Advances ◽  
2015 ◽  
Vol 5 (8) ◽  
pp. 5879-5885 ◽  
Author(s):  
Nuttapol Risangud ◽  
Zhijian Li ◽  
Athina Anastasaki ◽  
Paul Wilson ◽  
Kristian Kempe ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Polymer Synthesis ◽  
Late Transition Metal ◽  
Efficient Tool ◽  
Silicon Compounds ◽  
Late Transition

Hydrosilylation is a well-established reaction for the preparation of organo-silicon compounds, in which vinyl groups react with silanes (Si–H) usually catalysed by late transition metal complexes, most often Pt(ii) complexes.

Electron-density distributions in selected ferrocenyl-pyrazolyl late transition-metal complexes

2018 ◽  
Vol 20 (17) ◽  
pp. 11682-11691
Author(s):  
M. A. Peck ◽  
G. R. Hearne ◽  
C. Obuah ◽  
J. Darkwa
Keyword(s):  
Mössbauer Spectroscopy ◽  
Transition Metal ◽  
Metal Complexes ◽  
Electron Density ◽  
Transition Metal Complexes ◽  
Mossbauer Spectroscopy ◽  
Late Transition Metal ◽  
Density Distributions ◽  
Mößbauer Spectroscopy ◽  
Late Transition

57Fe Mössbauer spectroscopy has been used to study electronic dispersions in complexes of Fe, Co, Ni and Pd anchored onto 3-ferrocenyl-5-methylpyrazolylmethylenepyridine and 3-ferrocenylpyrazolylmethylenepyridine ligands.

Übergangsmetallkomplexe mit Schwefelliganden, LXXIII. Diastereospezifische Dichlormethylierung schwefelreicher [RuII(SRR′)(PPh3)′S4]-Komplexe (SRR′ = einzähniger Thioether- oder Thiol-Ligand; ′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethan(2-)) / Transition Metal Complexes with Sulfur Ligands, LXXIII. Diastereospecific Dichloromethylation of Sulfur Rich [RuII(SRR′)(PPh3)′S4] Complexes (SRR′ = Monodentate Thioether or Thiol Ligand;′S4′2- = 1,2-Bis(2-mercaptophenylthio)ethane(2-))

1991 ◽  
Vol 46 (12) ◽  
pp. 1585-1592 ◽  
Author(s):  
Dieter Sellmann ◽  
Peter Lechner ◽  
Falk Knoch ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Molecular Structures ◽  
X Ray ◽  
X Ray Crystallography ◽  
Thiol Ligand

Under exclusion of air the thioether and thiol complexes [Ru(SRR′)(PPh3)′S4′] (′S4′2- = 1,2-bis(2-mercaptophenylthio)ethane (2—)) easily react with CHCl3 yielding [Ru(Cl)(PPh3)(′S4′—CHCl2)] in which one thiolato atom of the ′S4′ ligand is diastereospecifically dichloromethylated. In the presence of air, however, [RuIII(Cl)(PPh3)′S4′] is formed.The molecular structures of [Ru(Cl)(PPh3)(′S4′-CHCl2)] · 2CHCl3 and [RuIII(Cl)(PPh3)′buS4′] have been determined by X-ray crystallography. ′buS4′2- (= 1,2-bis(3,5-di(t-butyl)-2-mercaptophenylthio)ethane(2-)) is the t-butyl derivative of the ′S4′ ligand. Reasons for observed diastereospecifity of alkylation are discussed.

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