Organometallic chemistry of Ga+: Formation of an unusual gallium dimer in the coordination sphere of ruthenium

Thomas Cadenbach; Christian Gemel; Timo Bollermann; Israel Fernandez; Gernot Frenking; Roland A. Fischer

doi:10.1002/chem.200801328

Organometallic chemistry of Ga⁺: Formation of an unusual gallium dimer in the coordination sphere of ruthenium

Thomas Cadenbach
, Christian Gemel
, Timo Bollermann
, Israel Fernandez
, Gernot Frenking
, Roland A. Fischer

Ruhr-Universität Bochum
Departamento de Parasitología, Facultad de Farmacia, Universidad Complutense de Madrid
University of Marburg

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

New insights into the distinct organometallic chemistry of the Ga ⁺ ion are presented. Ga⁺ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH₂) ₃^2-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)₃- [η³-(CH₂)₂C{CH₂(μ-Ga)}]} ₂][(BAr^F)₂] (4) (Cp* = C ₅Me₅, [BAr^F] = [B{C₆H ₃-(CF₃)₂}₄]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga⁺ as a ligand was found in the compound [Ru(PCy₃)₂(GaCp*)₂(Ga)][BAr ^F] (6) (Cy = C₆H₁₁, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga⁺ represents a pure σ/π-accepting ligand in this case.

Original language	English
Pages (from-to)	10789-10796
Number of pages	8
Journal	Chemistry - A European Journal
Volume	14
Issue number	34
DOIs	https://doi.org/10.1002/chem.200801328
State	Published - 26 Nov 2008
Externally published	Yes

Keywords

Density functional calculations
Gallium
Low-valent ion
Metal-metal interactions
Ruthenium

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10.1002/chem.200801328

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@article{fb594648053f4a568e7855809c4581f0,

title = "Organometallic chemistry of Ga+: Formation of an unusual gallium dimer in the coordination sphere of ruthenium",

abstract = "New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting {"}gallamethylallyl{"} ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C\{CH2(μ-Ga)\}]\} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B\{C6H 3-(CF3)2\}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case.",

keywords = "Density functional calculations, Gallium, Low-valent ion, Metal-metal interactions, Ruthenium",

author = "Thomas Cadenbach and Christian Gemel and Timo Bollermann and Israel Fernandez and Gernot Frenking and Fischer, \{Roland A.\}",

year = "2008",

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doi = "10.1002/chem.200801328",

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publisher = "John Wiley and Sons Inc",

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TY - JOUR

T1 - Organometallic chemistry of Ga+

T2 - Formation of an unusual gallium dimer in the coordination sphere of ruthenium

AU - Cadenbach, Thomas

AU - Gemel, Christian

AU - Bollermann, Timo

AU - Fernandez, Israel

AU - Frenking, Gernot

AU - Fischer, Roland A.

PY - 2008/11/26

Y1 - 2008/11/26

N2 - New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C{CH2(μ-Ga)}]} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B{C6H 3-(CF3)2}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case.

AB - New insights into the distinct organometallic chemistry of the Ga + ion are presented. Ga+ reacts as a strong electrophile with the electron rich ligand trismethylene-methane (C(CH2) 32-) attached at Ru by insertion into a Ru-C bond. The resulting "gallamethylallyl" ligand behaves like strong nucleophile similar to known monovalent GaR species. This donor property leads to the dimeric structure of the product [ (Ru(GaCp*)3- [η3-(CH2)2C{CH2(μ-Ga)}]} 2][(BArF)2] (4) (Cp* = C 5Me5, [BArF] = [B{C6H 3-(CF3)2}4]). Very unexpectedly, the two gallium ligands in this dimer are found in close vicinity to each other with a distance in the range of Ga-Ga bonds. Indeed, AIM calculations confirm a weak attractive closed shell Ga-Ga interaction. Finally, a novel example of a complex with substituent-free Ga+ as a ligand was found in the compound [Ru(PCy3)2(GaCp*)2(Ga)][BAr F] (6) (Cy = C6H11, cyclohexyl), the very short Ru-Ga bond length confirming the assumption that Ga+ represents a pure σ/π-accepting ligand in this case.

KW - Density functional calculations

KW - Gallium

KW - Low-valent ion

KW - Metal-metal interactions

KW - Ruthenium

UR - https://www.scopus.com/pages/publications/56749091493

U2 - 10.1002/chem.200801328

DO - 10.1002/chem.200801328

M3 - Artículo

AN - SCOPUS:56749091493

SN - 0947-6539

VL - 14

SP - 10789

EP - 10796

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 34

ER -

Organometallic chemistry of Ga⁺: Formation of an unusual gallium dimer in the coordination sphere of ruthenium

Abstract

Keywords

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