Group 9 Chalcogenometalates

Thomas E. Albrecht-Schmitt; James A. Ibers

doi:10.1021/ic960589w

Group 9 Chalcogenometalates

Thomas E. Albrecht-Schmitt, James A. Ibers^*

^*Corresponding author for this work

Chemistry

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

9 Scopus citations

Abstract

The compounds [K(18-crown-6)]₃[Ir(Se₄)₃] (1), [K(2.2.2-cryptand)]₃[Ir(Se₄)₃]·C ₆H₅CH₃ (2), and [K(18-crown-6)(DMF)₂][Ir(NCCH₃)₂(Se ₄)₂] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH₃)₂(COE)₂][BF₄] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH₃)₂(COE)₂][BF₄] as a Rh source produce homologues of the Ir complexes; these have been characterized by ⁷⁷Se NMR spectroscopy. [NH₄]₃[Ir(S₆)₃·H ₂O·0.5CH₃CH₂OH (4) has been synthesized from the reaction of IrCl₃·nH₂O with aqueous (NH₄)₂S_m. In the structure of [K(18-crown-6)]₃[Ir(Se₄)₃] (1) the Ir(III) center is chelated by three Se₄^2- ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Δλλλ and Δδδδ conformers. The K⁺ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(Se₄)₃]^3- anion. [K(2.2.2-cryptand)]₃[Ir(Se₄)₃]·C ₆H₅CH₃ (2) possesses no short K⋯Se interactions; here the [Ir(Se₄)₃]^3- anion crystallizes as the Δλλδ/Δδδλ racemate. In the crystal structure of [K(18-crown-6)(DMF)₂][Ir(NCCH₃)₂(Se ₄)₂] (3), the K⁺ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se₄^2- chains and two trans acetonitrile groups. The [Ir(Se₄)₃]^3- and [Rh(Se₄)₃]^3- anions undergo conformational transformations as a function of temperature, as observed by ⁷⁷Se NMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se₄)₃]^3-, ΔH = 2.5(5) kcal mol^-1, ΔS = 11.5(2.2) eu; [Rh(Se₄)₃]^3-, ΔH = 5.2(7) kcal mol^-1, ΔS = 24.7(3.0) eu.

Original language	English (US)
Pages (from-to)	7273-7278
Number of pages	6
Journal	Inorganic chemistry
Volume	35
Issue number	25
DOIs	https://doi.org/10.1021/ic960589w
State	Published - 1996

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic960589w

Cite this

@article{59d51bd609ae4935893bb7279a7d3732,

title = "Group 9 Chalcogenometalates",

abstract = "The compounds [K(18-crown-6)]3[Ir(Se4)3] (1), [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2), and [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH3)2(COE)2][BF4] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH3)2(COE)2][BF4] as a Rh source produce homologues of the Ir complexes; these have been characterized by 77Se NMR spectroscopy. [NH4]3[Ir(S6)3·H 2O·0.5CH3CH2OH (4) has been synthesized from the reaction of IrCl3·nH2O with aqueous (NH4)2Sm. In the structure of [K(18-crown-6)]3[Ir(Se4)3] (1) the Ir(III) center is chelated by three Se42- ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Δλλλ and Δδδδ conformers. The K+ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(Se4)3]3- anion. [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2) possesses no short K⋯Se interactions; here the [Ir(Se4)3]3- anion crystallizes as the Δλλδ/Δδδλ racemate. In the crystal structure of [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3), the K+ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se42- chains and two trans acetonitrile groups. The [Ir(Se4)3]3- and [Rh(Se4)3]3- anions undergo conformational transformations as a function of temperature, as observed by 77Se NMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se4)3]3-, ΔH = 2.5(5) kcal mol-1, ΔS = 11.5(2.2) eu; [Rh(Se4)3]3-, ΔH = 5.2(7) kcal mol-1, ΔS = 24.7(3.0) eu.",

author = "Albrecht-Schmitt, {Thomas E.} and Ibers, {James A.}",

year = "1996",

doi = "10.1021/ic960589w",

language = "English (US)",

volume = "35",

pages = "7273--7278",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "25",

}

TY - JOUR

T1 - Group 9 Chalcogenometalates

AU - Albrecht-Schmitt, Thomas E.

AU - Ibers, James A.

PY - 1996

Y1 - 1996

N2 - The compounds [K(18-crown-6)]3[Ir(Se4)3] (1), [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2), and [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH3)2(COE)2][BF4] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH3)2(COE)2][BF4] as a Rh source produce homologues of the Ir complexes; these have been characterized by 77Se NMR spectroscopy. [NH4]3[Ir(S6)3·H 2O·0.5CH3CH2OH (4) has been synthesized from the reaction of IrCl3·nH2O with aqueous (NH4)2Sm. In the structure of [K(18-crown-6)]3[Ir(Se4)3] (1) the Ir(III) center is chelated by three Se42- ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Δλλλ and Δδδδ conformers. The K+ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(Se4)3]3- anion. [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2) possesses no short K⋯Se interactions; here the [Ir(Se4)3]3- anion crystallizes as the Δλλδ/Δδδλ racemate. In the crystal structure of [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3), the K+ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se42- chains and two trans acetonitrile groups. The [Ir(Se4)3]3- and [Rh(Se4)3]3- anions undergo conformational transformations as a function of temperature, as observed by 77Se NMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se4)3]3-, ΔH = 2.5(5) kcal mol-1, ΔS = 11.5(2.2) eu; [Rh(Se4)3]3-, ΔH = 5.2(7) kcal mol-1, ΔS = 24.7(3.0) eu.

AB - The compounds [K(18-crown-6)]3[Ir(Se4)3] (1), [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2), and [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3) (DMF = dimethylformamide) have been prepared from the reaction of [Ir(NCCH3)2(COE)2][BF4] (COE = cyclooctene) with polyselenide anions in acetonitrile/DMF. Analogous reactions utilizing [Rh(NCCH3)2(COE)2][BF4] as a Rh source produce homologues of the Ir complexes; these have been characterized by 77Se NMR spectroscopy. [NH4]3[Ir(S6)3·H 2O·0.5CH3CH2OH (4) has been synthesized from the reaction of IrCl3·nH2O with aqueous (NH4)2Sm. In the structure of [K(18-crown-6)]3[Ir(Se4)3] (1) the Ir(III) center is chelated by three Se42- ligands to form a distorted octahedral anion. The structure contains a disordered racemate of the Δλλλ and Δδδδ conformers. The K+ cations are pulled out of the planes of the crowns and interact with Se atoms of the [Ir(Se4)3]3- anion. [K(2.2.2-cryptand)]3[Ir(Se4)3]·C 6H5CH3 (2) possesses no short K⋯Se interactions; here the [Ir(Se4)3]3- anion crystallizes as the Δλλδ/Δδδλ racemate. In the crystal structure of [K(18-crown-6)(DMF)2][Ir(NCCH3)2(Se 4)2] (3), the K+ cation is coordinated by an 18-crown-6 ligand and two DMF molecules and the anion comprises an octahedral Ir(III) center bound by two chelating Se42- chains and two trans acetonitrile groups. The [Ir(Se4)3]3- and [Rh(Se4)3]3- anions undergo conformational transformations as a function of temperature, as observed by 77Se NMR spectroscopy. The thermodynamics of these transformations are: [Ir(Se4)3]3-, ΔH = 2.5(5) kcal mol-1, ΔS = 11.5(2.2) eu; [Rh(Se4)3]3-, ΔH = 5.2(7) kcal mol-1, ΔS = 24.7(3.0) eu.

UR - http://www.scopus.com/inward/record.url?scp=0000314869&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000314869&partnerID=8YFLogxK

U2 - 10.1021/ic960589w

DO - 10.1021/ic960589w

M3 - Article

C2 - 11666918

AN - SCOPUS:0000314869

SN - 0020-1669

VL - 35

SP - 7273

EP - 7278

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 25

ER -

Group 9 Chalcogenometalates

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this