Characterization of Protonated trans Bis(dioxime) ruthenium Complexes: Crystal Structures of trans-Ru(DPGH)2(NO)Cl, trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl, and trans-Ru(DMGH)2(NO)Cl

Lisa F. Szczepura; James G. Muller; Carol A. Bessel; Ronald F. See; Thomas S. Janik; Melvyn Rowen Churchill; Kenneth J. Takeuchi

doi:10.1021/ic00031a031

Characterization of Protonated trans Bis(dioxime) ruthenium Complexes: Crystal Structures of trans-Ru(DPGH)₂(NO)Cl, trans-[Ru(DMGH)(DMGH₂)(NO)Cl]Cl, and trans-Ru(DMGH)₂(NO)Cl

Lisa F. Szczepura
, James G. Muller
, Carol A. Bessel
, Ronald F. See
, Thomas S. Janik
, Melvyn Rowen Churchill
, Kenneth J. Takeuchi

Chemistry

SUNY Buffalo
State University of New York at Fredonia

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

39 Scopus citations

Abstract

Single-crystal X-ray diffraction studies were carried out on trans-Ru(DPGH)₂(NO)Cl (1), trans-[Ru(DMGH)(DMGH₂)-(NO)Cl]Cl (2), and trans-Ru(DMGH)₂(NO)Cl (3) (DMGH = dimethylglyoxime monoanion, DPGH = diphenylglyoxime monoanion). These represent the first crystal structures of trans-bis(dioxime) complexes containing ruthenium. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 10.459 (5) Å, b = 10.148 (4) Å, c = 26.673 (13) Å, β = 98.25 (4) Å, Z = 4, V = 2802 (2) Å³, and R = 4.83%. Complex 2 crystallizes in the monoclinic space group P2₁/c, with a = 13.8100 (10) Å, b= 10.095 (2) Å, c = 11.898 (2) Å, β = 100.780 (10) Å, Z = 4, V = 1629.4 (4) Å³, and R = 3.05%. Complex 3 crystallizes in the orthorhombic space group P2₁2₁2₁with a = 7.9920 (10) Å, b = 14.251 (2) Å, c = 24.666 (2) Å, Z = 8, V = 2809.1 (5) Å³, and R = 3.84%. The crystal structure determinations include the location and refinement of hydrogen atoms associated with the oxime oxygens. The existence of two types of hydrogen bonds (O-H-Cl hydrogen bonds and a symmetric O-H-O oxime bridge) associated with the oxime oxygen atoms of trans-[Ru(DMGH)(DMGH₂)(NO)Cl]Cl can be clearly demonstrated. Furthermore, the crystal structures of both trans-Ru(DPGH)₂(NO)Cl and trans-Ru(DMGH)₂(NO)Cl display a third type of hydrogen bonding (asymmetric O-H-O oxime bridge) involving the oxime oxygen atoms. Thus, three types of hydrogen bonding that were previously proposed for Jrani-bis(dioxime) transition metal complexes can be directly observed within these three structurally similar bis(dioxime)ruthenium complexes. In addition, we can now unambiguously assign the O-H stretching IR bands to the proper modes of hydrogen bridging. Temperature-dependent ¹H NMR spectroscopy of trans-[Ru(DMGH)-(DMGH₂)(NO)Cl]Cl was used to measure rate constants of proton exchange, which demonstrated that the solid-state structure is maintained in solution. Finally, the cyclic voltammograms of complexes 2 and 3 and the pK_avalues for the stepwise removal of two protons from complex 2 were measured.

Original language	English
Pages (from-to)	859-869
Number of pages	11
Journal	Inorganic Chemistry
Volume	31
Issue number	5
DOIs	https://doi.org/10.1021/ic00031a031
State	Published - Mar 1 1992

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@article{8b8b5568823844f9a2a45ad227d90c5f,

title = "Characterization of Protonated trans Bis(dioxime) ruthenium Complexes: Crystal Structures of trans-Ru(DPGH)2(NO)Cl, trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl, and trans-Ru(DMGH)2(NO)Cl",

abstract = "Single-crystal X-ray diffraction studies were carried out on trans-Ru(DPGH)2(NO)Cl (1), trans-[Ru(DMGH)(DMGH2)-(NO)Cl]Cl (2), and trans-Ru(DMGH)2(NO)Cl (3) (DMGH = dimethylglyoxime monoanion, DPGH = diphenylglyoxime monoanion). These represent the first crystal structures of trans-bis(dioxime) complexes containing ruthenium. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 10.459 (5) {\AA}, b = 10.148 (4) {\AA}, c = 26.673 (13) {\AA}, β = 98.25 (4) {\AA}, Z = 4, V = 2802 (2) {\AA}3, and R = 4.83\%. Complex 2 crystallizes in the monoclinic space group P21/c, with a = 13.8100 (10) {\AA}, b= 10.095 (2) {\AA}, c = 11.898 (2) {\AA}, β = 100.780 (10) {\AA}, Z = 4, V = 1629.4 (4) {\AA}3, and R = 3.05\%. Complex 3 crystallizes in the orthorhombic space group P212121with a = 7.9920 (10) {\AA}, b = 14.251 (2) {\AA}, c = 24.666 (2) {\AA}, Z = 8, V = 2809.1 (5) {\AA}3, and R = 3.84\%. The crystal structure determinations include the location and refinement of hydrogen atoms associated with the oxime oxygens. The existence of two types of hydrogen bonds (O-H-Cl hydrogen bonds and a symmetric O-H-O oxime bridge) associated with the oxime oxygen atoms of trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl can be clearly demonstrated. Furthermore, the crystal structures of both trans-Ru(DPGH)2(NO)Cl and trans-Ru(DMGH)2(NO)Cl display a third type of hydrogen bonding (asymmetric O-H-O oxime bridge) involving the oxime oxygen atoms. Thus, three types of hydrogen bonding that were previously proposed for Jrani-bis(dioxime) transition metal complexes can be directly observed within these three structurally similar bis(dioxime)ruthenium complexes. In addition, we can now unambiguously assign the O-H stretching IR bands to the proper modes of hydrogen bridging. Temperature-dependent 1H NMR spectroscopy of trans-[Ru(DMGH)-(DMGH2)(NO)Cl]Cl was used to measure rate constants of proton exchange, which demonstrated that the solid-state structure is maintained in solution. Finally, the cyclic voltammograms of complexes 2 and 3 and the pKavalues for the stepwise removal of two protons from complex 2 were measured.",

author = "Szczepura, \{Lisa F.\} and Muller, \{James G.\} and Bessel, \{Carol A.\} and See, \{Ronald F.\} and Janik, \{Thomas S.\} and Churchill, \{Melvyn Rowen\} and Takeuchi, \{Kenneth J.\}",

year = "1992",

month = mar,

day = "1",

doi = "10.1021/ic00031a031",

language = "English",

volume = "31",

pages = "859--869",

journal = "Inorganic Chemistry",

issn = "0020-1669",

number = "5",

}

Characterization of Protonated trans Bis(dioxime) ruthenium Complexes: Crystal Structures of trans-Ru(DPGH)₂(NO)Cl, trans-[Ru(DMGH)(DMGH₂)(NO)Cl]Cl, and trans-Ru(DMGH)₂(NO)Cl. / Szczepura, Lisa F.; Muller, James G.; Bessel, Carol A. et al.
In: Inorganic Chemistry, Vol. 31, No. 5, 01.03.1992, p. 859-869.

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

TY - JOUR

T1 - Characterization of Protonated trans Bis(dioxime) ruthenium Complexes

T2 - Crystal Structures of trans-Ru(DPGH)2(NO)Cl, trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl, and trans-Ru(DMGH)2(NO)Cl

AU - Szczepura, Lisa F.

AU - Muller, James G.

AU - Bessel, Carol A.

AU - See, Ronald F.

AU - Janik, Thomas S.

AU - Churchill, Melvyn Rowen

AU - Takeuchi, Kenneth J.

PY - 1992/3/1

Y1 - 1992/3/1

N2 - Single-crystal X-ray diffraction studies were carried out on trans-Ru(DPGH)2(NO)Cl (1), trans-[Ru(DMGH)(DMGH2)-(NO)Cl]Cl (2), and trans-Ru(DMGH)2(NO)Cl (3) (DMGH = dimethylglyoxime monoanion, DPGH = diphenylglyoxime monoanion). These represent the first crystal structures of trans-bis(dioxime) complexes containing ruthenium. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 10.459 (5) Å, b = 10.148 (4) Å, c = 26.673 (13) Å, β = 98.25 (4) Å, Z = 4, V = 2802 (2) Å3, and R = 4.83%. Complex 2 crystallizes in the monoclinic space group P21/c, with a = 13.8100 (10) Å, b= 10.095 (2) Å, c = 11.898 (2) Å, β = 100.780 (10) Å, Z = 4, V = 1629.4 (4) Å3, and R = 3.05%. Complex 3 crystallizes in the orthorhombic space group P212121with a = 7.9920 (10) Å, b = 14.251 (2) Å, c = 24.666 (2) Å, Z = 8, V = 2809.1 (5) Å3, and R = 3.84%. The crystal structure determinations include the location and refinement of hydrogen atoms associated with the oxime oxygens. The existence of two types of hydrogen bonds (O-H-Cl hydrogen bonds and a symmetric O-H-O oxime bridge) associated with the oxime oxygen atoms of trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl can be clearly demonstrated. Furthermore, the crystal structures of both trans-Ru(DPGH)2(NO)Cl and trans-Ru(DMGH)2(NO)Cl display a third type of hydrogen bonding (asymmetric O-H-O oxime bridge) involving the oxime oxygen atoms. Thus, three types of hydrogen bonding that were previously proposed for Jrani-bis(dioxime) transition metal complexes can be directly observed within these three structurally similar bis(dioxime)ruthenium complexes. In addition, we can now unambiguously assign the O-H stretching IR bands to the proper modes of hydrogen bridging. Temperature-dependent 1H NMR spectroscopy of trans-[Ru(DMGH)-(DMGH2)(NO)Cl]Cl was used to measure rate constants of proton exchange, which demonstrated that the solid-state structure is maintained in solution. Finally, the cyclic voltammograms of complexes 2 and 3 and the pKavalues for the stepwise removal of two protons from complex 2 were measured.

AB - Single-crystal X-ray diffraction studies were carried out on trans-Ru(DPGH)2(NO)Cl (1), trans-[Ru(DMGH)(DMGH2)-(NO)Cl]Cl (2), and trans-Ru(DMGH)2(NO)Cl (3) (DMGH = dimethylglyoxime monoanion, DPGH = diphenylglyoxime monoanion). These represent the first crystal structures of trans-bis(dioxime) complexes containing ruthenium. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 10.459 (5) Å, b = 10.148 (4) Å, c = 26.673 (13) Å, β = 98.25 (4) Å, Z = 4, V = 2802 (2) Å3, and R = 4.83%. Complex 2 crystallizes in the monoclinic space group P21/c, with a = 13.8100 (10) Å, b= 10.095 (2) Å, c = 11.898 (2) Å, β = 100.780 (10) Å, Z = 4, V = 1629.4 (4) Å3, and R = 3.05%. Complex 3 crystallizes in the orthorhombic space group P212121with a = 7.9920 (10) Å, b = 14.251 (2) Å, c = 24.666 (2) Å, Z = 8, V = 2809.1 (5) Å3, and R = 3.84%. The crystal structure determinations include the location and refinement of hydrogen atoms associated with the oxime oxygens. The existence of two types of hydrogen bonds (O-H-Cl hydrogen bonds and a symmetric O-H-O oxime bridge) associated with the oxime oxygen atoms of trans-[Ru(DMGH)(DMGH2)(NO)Cl]Cl can be clearly demonstrated. Furthermore, the crystal structures of both trans-Ru(DPGH)2(NO)Cl and trans-Ru(DMGH)2(NO)Cl display a third type of hydrogen bonding (asymmetric O-H-O oxime bridge) involving the oxime oxygen atoms. Thus, three types of hydrogen bonding that were previously proposed for Jrani-bis(dioxime) transition metal complexes can be directly observed within these three structurally similar bis(dioxime)ruthenium complexes. In addition, we can now unambiguously assign the O-H stretching IR bands to the proper modes of hydrogen bridging. Temperature-dependent 1H NMR spectroscopy of trans-[Ru(DMGH)-(DMGH2)(NO)Cl]Cl was used to measure rate constants of proton exchange, which demonstrated that the solid-state structure is maintained in solution. Finally, the cyclic voltammograms of complexes 2 and 3 and the pKavalues for the stepwise removal of two protons from complex 2 were measured.

UR - https://www.scopus.com/pages/publications/0001607377

U2 - 10.1021/ic00031a031

DO - 10.1021/ic00031a031

M3 - Article

AN - SCOPUS:0001607377

SN - 0020-1669

VL - 31

SP - 859

EP - 869

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 5

ER -

Characterization of Protonated trans Bis(dioxime) ruthenium Complexes: Crystal Structures of trans-Ru(DPGH)₂(NO)Cl, trans-[Ru(DMGH)(DMGH₂)(NO)Cl]Cl, and trans-Ru(DMGH)₂(NO)Cl

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