Ligand sphere conversions in terminal carbide complexes

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Standard

Ligand sphere conversions in terminal carbide complexes. / Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.; Bendix, Jesper.

I: Organometallics, Bind 35, Nr. 2, 2016, s. 100-105.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt

Harvard

Morsing, TJ, Reinholdt, A, Sauer, SPA & Bendix, J 2016, 'Ligand sphere conversions in terminal carbide complexes', Organometallics, bind 35, nr. 2, s. 100-105. https://doi.org/10.1021/acs.organomet.5b00803

APA

Morsing, T. J., Reinholdt, A., Sauer, S. P. A., & Bendix, J. (2016). Ligand sphere conversions in terminal carbide complexes. Organometallics, 35(2), 100-105. https://doi.org/10.1021/acs.organomet.5b00803

Vancouver

Morsing TJ, Reinholdt A, Sauer SPA, Bendix J. Ligand sphere conversions in terminal carbide complexes. Organometallics. 2016;35(2):100-105. https://doi.org/10.1021/acs.organomet.5b00803

Author

Morsing, Thorbjørn Juul ; Reinholdt, Anders ; Sauer, Stephan P. A. ; Bendix, Jesper. / Ligand sphere conversions in terminal carbide complexes. I: Organometallics. 2016 ; Bind 35, Nr. 2. s. 100-105.

Bibtex

@article{24cd806b2ad34cc5b69492ad516fb341,
title = "Ligand sphere conversions in terminal carbide complexes",
abstract = "Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) M–1 s–1. Further reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN)4(PCy3)2]2–, which was isolated and structurally characterized as its PPh4+ salt.",
author = "Morsing, {Thorbj{\o}rn Juul} and Anders Reinholdt and Sauer, {Stephan P. A.} and Jesper Bendix",
year = "2016",
doi = "10.1021/acs.organomet.5b00803",
language = "English",
volume = "35",
pages = "100--105",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "2",

}

RIS

TY - JOUR

T1 - Ligand sphere conversions in terminal carbide complexes

AU - Morsing, Thorbjørn Juul

AU - Reinholdt, Anders

AU - Sauer, Stephan P. A.

AU - Bendix, Jesper

PY - 2016

Y1 - 2016

N2 - Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) M–1 s–1. Further reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN)4(PCy3)2]2–, which was isolated and structurally characterized as its PPh4+ salt.

AB - Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction found to be quite sluggish and of first order in both RuC and cyanide with a rate constant of k = 0.0104(6) M–1 s–1. Further reaction with cyanide leads to loss of the carbide ligand and formation of trans-[Ru(CN)4(PCy3)2]2–, which was isolated and structurally characterized as its PPh4+ salt.

U2 - 10.1021/acs.organomet.5b00803

DO - 10.1021/acs.organomet.5b00803

M3 - Journal article

VL - 35

SP - 100

EP - 105

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 2

ER -

ID: 154179789