Synthesis and characterization of the first series of isolable (nitro)ruthenium(III) complexes: A decomposition mechanism of the (nitro)ruthenium(III) moiety

Randolph A. Leising; Stephen A. Kubow; Lisa F. Szczepura; Kenneth J. Takeuchi

doi:10.1016/0020-1693(95)04808-1

Synthesis and characterization of the first series of isolable (nitro)ruthenium(III) complexes: A decomposition mechanism of the (nitro)ruthenium(III) moiety

Randolph A. Leising
, Stephen A. Kubow
, Lisa F. Szczepura
, Kenneth J. Takeuchi

Chemistry

SUNY Buffalo
Kean University

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

16 Scopus citations

Abstract

The first series of isolable (nitro)ruthenium(III) complexes were prepared by the chemical oxidation of trans-[Ru(NO₂)(PR₃)₂(trpy)]⁺ (R = methyl (Me), ethyl (Et), and n-propyl (n-Pr)) and trans-[Ru(NO₂)(PMe₃)(PR₃)(trpy)]⁺ (R = Et and n-Pr). These complexes were characterized by elemental analysis, cyclic voltammetry, UV-Vis spectroscopy and magnetic susceptibility. A study of the decomposition reactions of these complexes in acetonitrile at 25 °C was undertaken, where the products were identified by UV-Vis spectroscopy and cyclic voltammetry. The product distribution changed from a 1:1:1 ratio of [Ru(NO)(PR₃)₂(rpy)]³⁺:[Ru(NO ₃)(PR₃)_2- (trpy)]²⁺:[Ru(NO₂)(PR₃)₂(trpy)] ⁺ to a 1:1 ratio of [Ru(NO)(PR₃)₂(trpy)]³⁺:[Ru(NO ₃)(PR₃)₂(trpy)]⁺ depending on the R group of the PR₃ ligands. The electrochemical data, combined with an ¹⁵NO₂IR spectroscopic labeling study on the most and least stable complexes in the series, suggests the decomposition mechanism involves nitro-nitrito linkage isomerization, followed by the formation of a transitory dimeric species that breaks apart into the final products.

Original language	English
Pages (from-to)	167-176
Number of pages	10
Journal	Inorganica Chimica Acta
Volume	245
Issue number	2
DOIs	https://doi.org/10.1016/0020-1693(95)04808-1
State	Published - Apr 15 1996

Keywords

Decomposition mechanism
Nitro complexes
Ruthenium complexes

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10.1016/0020-1693(95)04808-1

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@article{4552eb0913014306aee796db711677fb,

title = "Synthesis and characterization of the first series of isolable (nitro)ruthenium(III) complexes: A decomposition mechanism of the (nitro)ruthenium(III) moiety",

abstract = "The first series of isolable (nitro)ruthenium(III) complexes were prepared by the chemical oxidation of trans-[Ru(NO2)(PR3)2(trpy)]+ (R = methyl (Me), ethyl (Et), and n-propyl (n-Pr)) and trans-[Ru(NO2)(PMe3)(PR3)(trpy)]+ (R = Et and n-Pr). These complexes were characterized by elemental analysis, cyclic voltammetry, UV-Vis spectroscopy and magnetic susceptibility. A study of the decomposition reactions of these complexes in acetonitrile at 25 °C was undertaken, where the products were identified by UV-Vis spectroscopy and cyclic voltammetry. The product distribution changed from a 1:1:1 ratio of [Ru(NO)(PR3)2(rpy)]3+:[Ru(NO 3)(PR3)2- (trpy)]2+:[Ru(NO2)(PR3)2(trpy)] + to a 1:1 ratio of [Ru(NO)(PR3)2(trpy)]3+:[Ru(NO 3)(PR3)2(trpy)]+ depending on the R group of the PR3 ligands. The electrochemical data, combined with an 15NO2IR spectroscopic labeling study on the most and least stable complexes in the series, suggests the decomposition mechanism involves nitro-nitrito linkage isomerization, followed by the formation of a transitory dimeric species that breaks apart into the final products.",

keywords = "Decomposition mechanism, Nitro complexes, Ruthenium complexes",

author = "Leising, \{Randolph A.\} and Kubow, \{Stephen A.\} and Szczepura, \{Lisa F.\} and Takeuchi, \{Kenneth J.\}",

year = "1996",

month = apr,

day = "15",

doi = "10.1016/0020-1693(95)04808-1",

language = "English",

volume = "245",

pages = "167--176",

journal = "Inorganica Chimica Acta",

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TY - JOUR

T1 - Synthesis and characterization of the first series of isolable (nitro)ruthenium(III) complexes

T2 - A decomposition mechanism of the (nitro)ruthenium(III) moiety

AU - Leising, Randolph A.

AU - Kubow, Stephen A.

AU - Szczepura, Lisa F.

AU - Takeuchi, Kenneth J.

PY - 1996/4/15

Y1 - 1996/4/15

N2 - The first series of isolable (nitro)ruthenium(III) complexes were prepared by the chemical oxidation of trans-[Ru(NO2)(PR3)2(trpy)]+ (R = methyl (Me), ethyl (Et), and n-propyl (n-Pr)) and trans-[Ru(NO2)(PMe3)(PR3)(trpy)]+ (R = Et and n-Pr). These complexes were characterized by elemental analysis, cyclic voltammetry, UV-Vis spectroscopy and magnetic susceptibility. A study of the decomposition reactions of these complexes in acetonitrile at 25 °C was undertaken, where the products were identified by UV-Vis spectroscopy and cyclic voltammetry. The product distribution changed from a 1:1:1 ratio of [Ru(NO)(PR3)2(rpy)]3+:[Ru(NO 3)(PR3)2- (trpy)]2+:[Ru(NO2)(PR3)2(trpy)] + to a 1:1 ratio of [Ru(NO)(PR3)2(trpy)]3+:[Ru(NO 3)(PR3)2(trpy)]+ depending on the R group of the PR3 ligands. The electrochemical data, combined with an 15NO2IR spectroscopic labeling study on the most and least stable complexes in the series, suggests the decomposition mechanism involves nitro-nitrito linkage isomerization, followed by the formation of a transitory dimeric species that breaks apart into the final products.

AB - The first series of isolable (nitro)ruthenium(III) complexes were prepared by the chemical oxidation of trans-[Ru(NO2)(PR3)2(trpy)]+ (R = methyl (Me), ethyl (Et), and n-propyl (n-Pr)) and trans-[Ru(NO2)(PMe3)(PR3)(trpy)]+ (R = Et and n-Pr). These complexes were characterized by elemental analysis, cyclic voltammetry, UV-Vis spectroscopy and magnetic susceptibility. A study of the decomposition reactions of these complexes in acetonitrile at 25 °C was undertaken, where the products were identified by UV-Vis spectroscopy and cyclic voltammetry. The product distribution changed from a 1:1:1 ratio of [Ru(NO)(PR3)2(rpy)]3+:[Ru(NO 3)(PR3)2- (trpy)]2+:[Ru(NO2)(PR3)2(trpy)] + to a 1:1 ratio of [Ru(NO)(PR3)2(trpy)]3+:[Ru(NO 3)(PR3)2(trpy)]+ depending on the R group of the PR3 ligands. The electrochemical data, combined with an 15NO2IR spectroscopic labeling study on the most and least stable complexes in the series, suggests the decomposition mechanism involves nitro-nitrito linkage isomerization, followed by the formation of a transitory dimeric species that breaks apart into the final products.

KW - Decomposition mechanism

KW - Nitro complexes

KW - Ruthenium complexes

UR - https://www.scopus.com/pages/publications/0000806142

U2 - 10.1016/0020-1693(95)04808-1

DO - 10.1016/0020-1693(95)04808-1

M3 - Article

AN - SCOPUS:0000806142

SN - 0020-1693

VL - 245

SP - 167

EP - 176

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 2

ER -

Synthesis and characterization of the first series of isolable (nitro)ruthenium(III) complexes: A decomposition mechanism of the (nitro)ruthenium(III) moiety

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Keywords

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