A new class of (μ-η2:η2-disulfido) dicopper complexes: Synthesis, characterization, and disulfido exchange

Eric C. Brown; Nermeen W. Aboelella; Anne M. Reynolds; Gabriel Aullón; Santiago Alvarez; William B. Tolman

doi:10.1021/ic049811k

A new class of (μ-η²:η²-disulfido) dicopper complexes: Synthesis, characterization, and disulfido exchange

Eric C. Brown
, Nermeen W. Aboelella
, Anne M. Reynolds
, Gabriel Aullón
, Santiago Alvarez
, William B. Tolman

Chemistry Department

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

70 Scopus citations

Abstract

Rare examples of (μ-η²:η ²-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of β-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a β-diketiminate ligand was identified. DFT calculations on [(LCu) ₂X₂] (L = β-diketiminate, X = O or S) complexes rationalize the absence of a bis(μ-sulfido)dicopper isomer, [Cu ₂(μ-S)₂]²⁺, in the synthetic reactions, yet predict that a [Cu₂(μ-S)₂]⁰ core is a stable product of 2-electron reduction of the [Cu₂(μ-η ²:η²-S₂)]²⁺ unit. Exchange of the disulfido ligand was discovered upon reaction of a (μ-η²: η²-disulfido)dicopper complex with a Cu(I) reagent.

Original language	English
Pages (from-to)	3335-3337
Number of pages	3
Journal	Inorganic Chemistry
Volume	43
Issue number	11
DOIs	https://doi.org/10.1021/ic049811k
State	Published - 31 May 2004

Keywords

Copper/chemistry
Crystallography, X-Ray
Imines/chemistry
Ligands
Molecular Structure
Organometallic Compounds/chemical synthesis
Oxidation-Reduction
Oxygen/chemistry
Stereoisomerism
Sulfur/chemistry

Access to Document

10.1021/ic049811k

Cite this

@article{66174aadea004c128285eb0d4a261d4d,

title = "A new class of (μ-η2:η2-disulfido) dicopper complexes: Synthesis, characterization, and disulfido exchange",

abstract = "Rare examples of (μ-η2:η 2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of β-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a β-diketiminate ligand was identified. DFT calculations on [(LCu) 2X2] (L = β-diketiminate, X = O or S) complexes rationalize the absence of a bis(μ-sulfido)dicopper isomer, [Cu 2(μ-S)2]2+, in the synthetic reactions, yet predict that a [Cu2(μ-S)2]0 core is a stable product of 2-electron reduction of the [Cu2(μ-η 2:η2-S2)]2+ unit. Exchange of the disulfido ligand was discovered upon reaction of a (μ-η2: η2-disulfido)dicopper complex with a Cu(I) reagent.",

keywords = "Copper/chemistry, Crystallography, X-Ray, Imines/chemistry, Ligands, Molecular Structure, Organometallic Compounds/chemical synthesis, Oxidation-Reduction, Oxygen/chemistry, Stereoisomerism, Sulfur/chemistry",

author = "Brown, \{Eric C.\} and Aboelella, \{Nermeen W.\} and Reynolds, \{Anne M.\} and Gabriel Aull{\'o}n and Santiago Alvarez and Tolman, \{William B.\}",

year = "2004",

month = may,

day = "31",

doi = "10.1021/ic049811k",

language = "English",

volume = "43",

pages = "3335--3337",

number = "11",

}

TY - JOUR

T1 - A new class of (μ-η2:η2-disulfido) dicopper complexes

T2 - Synthesis, characterization, and disulfido exchange

AU - Brown, Eric C.

AU - Aboelella, Nermeen W.

AU - Reynolds, Anne M.

AU - Aullón, Gabriel

AU - Alvarez, Santiago

AU - Tolman, William B.

PY - 2004/5/31

Y1 - 2004/5/31

N2 - Rare examples of (μ-η2:η 2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of β-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a β-diketiminate ligand was identified. DFT calculations on [(LCu) 2X2] (L = β-diketiminate, X = O or S) complexes rationalize the absence of a bis(μ-sulfido)dicopper isomer, [Cu 2(μ-S)2]2+, in the synthetic reactions, yet predict that a [Cu2(μ-S)2]0 core is a stable product of 2-electron reduction of the [Cu2(μ-η 2:η2-S2)]2+ unit. Exchange of the disulfido ligand was discovered upon reaction of a (μ-η2: η2-disulfido)dicopper complex with a Cu(I) reagent.

AB - Rare examples of (μ-η2:η 2-disulfido)dicopper complexes have been prepared from Cu(I) and Cu(II) complexes of β-diketiminate and anilido-imine supporting ligands. A novel byproduct derived from sulfur functionalization of the methine position of a β-diketiminate ligand was identified. DFT calculations on [(LCu) 2X2] (L = β-diketiminate, X = O or S) complexes rationalize the absence of a bis(μ-sulfido)dicopper isomer, [Cu 2(μ-S)2]2+, in the synthetic reactions, yet predict that a [Cu2(μ-S)2]0 core is a stable product of 2-electron reduction of the [Cu2(μ-η 2:η2-S2)]2+ unit. Exchange of the disulfido ligand was discovered upon reaction of a (μ-η2: η2-disulfido)dicopper complex with a Cu(I) reagent.

KW - Copper/chemistry

KW - Crystallography, X-Ray

KW - Imines/chemistry

KW - Ligands

KW - Molecular Structure

KW - Organometallic Compounds/chemical synthesis

KW - Oxidation-Reduction

KW - Oxygen/chemistry

KW - Stereoisomerism

KW - Sulfur/chemistry

UR - https://www.scopus.com/pages/publications/2442644021

U2 - 10.1021/ic049811k

DO - 10.1021/ic049811k

M3 - Article

C2 - 15154793

AN - SCOPUS:2442644021

SN - 0020-1669

VL - 43

SP - 3335

EP - 3337

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 11

ER -

A new class of (μ-η²:η²-disulfido) dicopper complexes: Synthesis, characterization, and disulfido exchange

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this