Synthesis and Characterization of (Nitro)ruthenium Complexes That Utilize Identical Trans-Positioned Tertiary Phosphine Ligands

Randolph A. Leising; Stephen A. Kubow; Kenneth J. Takeuchi

doi:10.1021/ic00347a047

Synthesis and Characterization of (Nitro)ruthenium Complexes That Utilize Identical Trans-Positioned Tertiary Phosphine Ligands

Randolph A. Leising
, Stephen A. Kubow
, Kenneth J. Takeuchi

Chemistry

SUNY Buffalo

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

21 Scopus citations

Abstract

We report the synthesis and characterization of a variety of complexes with the form [Ru(NO₂)(PR₃)₂(trpy)](ClO₄) (trpy = 2,2′:6′,2″-terpyridine and PR₃= tertiary phosphine ligand, where R = ethyl, n-propyl, n-butyl, phenyl, and benzyl) and [Ru-(NO)(PR₃)₂(trpy)](ClO₄)₃. Two routes toward the synthesis of the [Ru(NO₂)(PR₃)₂(trpy)](ClO₄) complexes, starting from Ru(Cl)₃·3H₂O, will be discussed. One method involves a five-step synthesis, with the stepwise addition of the phosphine ligands. The other route, a three-step synthesis, involves a novel one-pot incorporation of two phosphine ligands into the trans positions of a ruthenium coordination center. Characterization of the [Ru(NO₂)(PR₃)₂(trpy)](ClO₄) complexes was accomplished through elemental analysis, IR, UV-visible, ¹H NMR, and ¹³C NMR spectroscopies, and cyclic voltammetry. Notably, variations in the phosphine ligands resulted in cyclic voltammograms that ranged from reversible to irreversible, where the utilization of trimethylphosphine resulted in the greatest reversibility. The irreversible voltammograms indicated that the electrochemically generated [Ru(NO2)(PR₁₂(trpy)]²⁺complexes were unstable and that the analogous [Ru(NO)(PR₃)₂(trpy)]³⁺complexes were the decomposition products. In this regard, we also report the synthesis and characterization of [Ru(NO)(PR₃)₂(trpy)](ClO₄)₃complexes, where the complexes were characterized by elemental analysis, IR and UV-visible spectroscopies, and cyclic voltammetry.

Original language	English
Pages (from-to)	4569-4574
Number of pages	6
Journal	Inorganic Chemistry
Volume	29
Issue number	22
DOIs	https://doi.org/10.1021/ic00347a047
State	Published - 1990

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@article{6481374b04ba4e98b032dc29ba1d560f,

title = "Synthesis and Characterization of (Nitro)ruthenium Complexes That Utilize Identical Trans-Positioned Tertiary Phosphine Ligands",

abstract = "We report the synthesis and characterization of a variety of complexes with the form [Ru(NO2)(PR3)2(trpy)](ClO4) (trpy = 2,2′:6′,2″-terpyridine and PR3= tertiary phosphine ligand, where R = ethyl, n-propyl, n-butyl, phenyl, and benzyl) and [Ru-(NO)(PR3)2(trpy)](ClO4)3. Two routes toward the synthesis of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes, starting from Ru(Cl)3·3H2O, will be discussed. One method involves a five-step synthesis, with the stepwise addition of the phosphine ligands. The other route, a three-step synthesis, involves a novel one-pot incorporation of two phosphine ligands into the trans positions of a ruthenium coordination center. Characterization of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes was accomplished through elemental analysis, IR, UV-visible, 1H NMR, and 13C NMR spectroscopies, and cyclic voltammetry. Notably, variations in the phosphine ligands resulted in cyclic voltammograms that ranged from reversible to irreversible, where the utilization of trimethylphosphine resulted in the greatest reversibility. The irreversible voltammograms indicated that the electrochemically generated [Ru(NO2)(PR12(trpy)]2+complexes were unstable and that the analogous [Ru(NO)(PR3)2(trpy)]3+complexes were the decomposition products. In this regard, we also report the synthesis and characterization of [Ru(NO)(PR3)2(trpy)](ClO4)3complexes, where the complexes were characterized by elemental analysis, IR and UV-visible spectroscopies, and cyclic voltammetry.",

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

year = "1990",

doi = "10.1021/ic00347a047",

language = "English",

volume = "29",

pages = "4569--4574",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "22",

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TY - JOUR

T1 - Synthesis and Characterization of (Nitro)ruthenium Complexes That Utilize Identical Trans-Positioned Tertiary Phosphine Ligands

AU - Leising, Randolph A.

AU - Kubow, Stephen A.

AU - Takeuchi, Kenneth J.

PY - 1990

Y1 - 1990

N2 - We report the synthesis and characterization of a variety of complexes with the form [Ru(NO2)(PR3)2(trpy)](ClO4) (trpy = 2,2′:6′,2″-terpyridine and PR3= tertiary phosphine ligand, where R = ethyl, n-propyl, n-butyl, phenyl, and benzyl) and [Ru-(NO)(PR3)2(trpy)](ClO4)3. Two routes toward the synthesis of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes, starting from Ru(Cl)3·3H2O, will be discussed. One method involves a five-step synthesis, with the stepwise addition of the phosphine ligands. The other route, a three-step synthesis, involves a novel one-pot incorporation of two phosphine ligands into the trans positions of a ruthenium coordination center. Characterization of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes was accomplished through elemental analysis, IR, UV-visible, 1H NMR, and 13C NMR spectroscopies, and cyclic voltammetry. Notably, variations in the phosphine ligands resulted in cyclic voltammograms that ranged from reversible to irreversible, where the utilization of trimethylphosphine resulted in the greatest reversibility. The irreversible voltammograms indicated that the electrochemically generated [Ru(NO2)(PR12(trpy)]2+complexes were unstable and that the analogous [Ru(NO)(PR3)2(trpy)]3+complexes were the decomposition products. In this regard, we also report the synthesis and characterization of [Ru(NO)(PR3)2(trpy)](ClO4)3complexes, where the complexes were characterized by elemental analysis, IR and UV-visible spectroscopies, and cyclic voltammetry.

AB - We report the synthesis and characterization of a variety of complexes with the form [Ru(NO2)(PR3)2(trpy)](ClO4) (trpy = 2,2′:6′,2″-terpyridine and PR3= tertiary phosphine ligand, where R = ethyl, n-propyl, n-butyl, phenyl, and benzyl) and [Ru-(NO)(PR3)2(trpy)](ClO4)3. Two routes toward the synthesis of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes, starting from Ru(Cl)3·3H2O, will be discussed. One method involves a five-step synthesis, with the stepwise addition of the phosphine ligands. The other route, a three-step synthesis, involves a novel one-pot incorporation of two phosphine ligands into the trans positions of a ruthenium coordination center. Characterization of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes was accomplished through elemental analysis, IR, UV-visible, 1H NMR, and 13C NMR spectroscopies, and cyclic voltammetry. Notably, variations in the phosphine ligands resulted in cyclic voltammograms that ranged from reversible to irreversible, where the utilization of trimethylphosphine resulted in the greatest reversibility. The irreversible voltammograms indicated that the electrochemically generated [Ru(NO2)(PR12(trpy)]2+complexes were unstable and that the analogous [Ru(NO)(PR3)2(trpy)]3+complexes were the decomposition products. In this regard, we also report the synthesis and characterization of [Ru(NO)(PR3)2(trpy)](ClO4)3complexes, where the complexes were characterized by elemental analysis, IR and UV-visible spectroscopies, and cyclic voltammetry.

UR - https://www.scopus.com/pages/publications/0010915042

U2 - 10.1021/ic00347a047

DO - 10.1021/ic00347a047

M3 - Article

AN - SCOPUS:0010915042

SN - 0020-1669

VL - 29

SP - 4569

EP - 4574

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Synthesis and Characterization of (Nitro)ruthenium Complexes That Utilize Identical Trans-Positioned Tertiary Phosphine Ligands

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