Orde Munro | University of the Witwatersrand (original) (raw)
Papers by Orde Munro
Journal of The American Chemical Society, 1995
A new molecular mechanics (MM) force field model for six-coordinate low-spin imidazole and pyridi... more A new molecular mechanics (MM) force field model for six-coordinate low-spin imidazole and pyridine complexes of ferric porphyrins has been used with a modified version of the program MM2(87) to investigate the planar and ruffled conformations of [Fe(TMP)(L)# complexes, where L = a pyridine or imidazole derivative. All currently available X-ray structures in this class were used to gauge parametrization of the force field, including that of [Fe(TMP)( 1,2-Me~Im)z]C104, whose preparation, Mossbauer spectrum, and X-ray structure determination are described. [Fe(TMP)(1,2-Me2Im)~]C104 has the most ruffled core of any iron(1II) porphyrin described to date, with mean absolute core atom displacements Ca, c b , C,, and C,, of 0.41, 0.28, 0.72, and 0.42 A, respectively. The average Fe-N,, distance is also the shortest observed at 1.937 A. The MM-calculated and crystallographically observed structures of [Fe(TMP)(1,2-MezIm)2]+ both show that the porphyrin core is distorted from ideal DZd symmetry in response to anisotropic distribution of steric bulk in the axial ligands. Our calculations indicate that Du-ruffling of the porphyrin core hinges on a relative perpendicular orientation for the axial ligands, with the magnitude of distortion increasing with increasing ligand bulk (4(5)-MeHIm < pyridine < 1,2-MezIm < BzHIm < 2-MeBzHIm). The MM and crystallographic data therefore demonstrate that ligand-porphyrin nonbonded interactions are the primary determinant of core conformation in six-coordinate complexes. Furthermore, the meso-mesityl groups of [Fe(TMP)-(L)# derivatives exhibit slightly staggered minimum-energy orientations that become more staggered with increasing axial ligand bulk, providing direct evidence for nonbonded interactions between the ligands and the peripheral substituents. Since counterrotation of a trans pair of mesityl groups in Du-ruf [Fe(TMP)(2-MeBzHIm)z]+ only scarcely perturbed the minimum-energy orientations of the axial ligands, by inducing slight changes in the symmetry of the core distortion and direct intramolecular contact, ligand-peripheral group interactions control the finer aspects of molecular conformation. In contrast, nonbonded interactions between the peripheral aryl groups and the porphyrin core were the primary determinant of core conformation in four-coordinate Dwsad [Fe(meso-tetraarylporphyrin)]+ species. The calculated core distortion increased with increasing size of the meso-aryl substituents (phenyl < < 2,6dichlorophenyl < mesityl). Crystal data for [Fe(TMP)( 1,2-Me2Im)~]ClO4.0.65Cd-I~Cl*l .05Hz0: a = 14.958(24) A, b = 21.147(21) A, c = 20.897(32) A, p = 98.98(12)", space group P21/n, V = 6529 A3, Z = 4, T = 127 K, number of observed data = 8473, R1 = 0.072, Rz = 0.088.
Journal of The American Chemical Society, 1997
ABSTRACT
Acta crystallographica. Section C, Crystal structure communications, 2010
The crystal structures of two para-substituted aryl derivatives of pyridine-2-carboxamide, namely... more The crystal structures of two para-substituted aryl derivatives of pyridine-2-carboxamide, namely N-(4-fluorophenyl)pyridine-2-carboxamide, C(12)H(9)FN(2)O, (I), and N-(4-nitrophenyl)pyridine-2-carboxamide, C(12)H(9)N(3)O(3), (II), have been studied. Compound (I) exhibits unconventional aryl-carbonyl C-H...O and pyridine-fluorine C-H...F hydrogen bonding in two dimensions and well defined π-stacking involving pyridine rings in the third dimension. The conformation of (II) is more nearly planar than that of (I) and the intermolecular interactions comprise one-dimensional aryl-carbonyl C-H...O hydrogen bonds leading to a stepped or staircase-like progression of loosely π-stacked molecules. The close-packed layers of planar π-stacked molecules are related by inversion symmetry. Two alternating interplanar separations of 3.439 (1) and 3.476 (1) Å are observed in the crystal lattice and are consistent with a repetitive packing sequence, ABA'B'AB…, for the π-stacked inversion pair...
Acta Crystallographica Section C Crystal Structure Communications, 2012
The cation of the title complex salt, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]pro... more The cation of the title complex salt, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]propane-1,3-diamine}platinum(II) tetrafluoridoborate, [PtCl(C(12)H(19)N(3))]BF(4), exhibits a nominally square-planar Pt(II) ion coordinated to a chloride ion [Pt-Cl = 2.3046 (9) Å] and three unique N-atom types, viz. pyridine, imine and amine, of the tridentate Schiff base ligand formed by the 1:1 condensation of 1-(pyridin-2-yl)ethanone and 2,2-dimethylpropane-1,3-diamine. The cations are π-stacked in inversion-related pairs (dimers), with a mean plane separation of 3.426 Å, an intradimer Pt···Pt separation of 5.0785 (6) Å and a lateral shift of 3.676 Å. The centroid (Cg) of the pyridine ring is positioned approximately over the Pt(II) ion of the neighbouring cation (Pt···Cg = 3.503 Å).
Inorganic chemistry, Jan 15, 2013
The structures, spectroscopy, and cytotoxicity of four novel nominally square-planar gold(III) ch... more The structures, spectroscopy, and cytotoxicity of four novel nominally square-planar gold(III) chelates 1-4 with the general formula cis-AuCl2(X), where the ligand X is an anionic bidentate pyridyl- or isoquinolylamido chelating agent, are described. The Au-N(amido), Au-N(pyridyl), and Au-N(isoquinolyl) distances are 2.002(9)-2.016(3), 2.01(1)-2.037(3), and 2.037(3) Å, respectively. Density functional theory simulations afforded accurate gold(III) coordination geometries for 1-4 (bond distances and angles to within 5% of the X-ray values), while accurate transition energies were limited to those calculated in the UV spectral region. The complexes had variable stability in dimethyl sulfoxide: compound 3 (relatively rigid) was indefinitely stable, compounds 1 and 2 (conformationally flexible) slowly demetalated over 30 days, and 4 (extensively aromatic) formed an insoluble precipitate after 10 days (72 h in an aqueous buffer). The isoquinolylamido derivative 4 was sufficiently cytotox...
Chemistry - A European Journal, 2014
A series of Group 7 Fischer carbene complexes, [Cp(CO) 2 Mn I = C(OEt)Ar] (Cp = cyclopentadienyl,... more A series of Group 7 Fischer carbene complexes, [Cp(CO) 2 Mn I = C(OEt)Ar] (Cp = cyclopentadienyl, Ar = Th = thienyl (1 a), Ar = Fu = furyl (2 a), Ar = Fc = ferrocenyl (3 a)) and biscarbene complexes, [Cp(CO) 2 Mn=C(OEt)ÀAr'À(OEt)C= Mn(CO) 2 Cp] (Ar' = Th' = 2,5-thienylene (1 b), Ar' = Fu' = 2,5furylene (2 b), Ar' = Fc' = 1,1'-ferrocendiyl (3 b)) was synthesized and characterized. Chemical oxidation of [Cp(CO) 2 Mn= C(OEt)Fc] (3 a) and isolation of the oxidised species [3 a][PF 6 ] possessing a Mn II centre proved possible below À30 8C in dichloromethane solution. The ESR spectrum of the transiently stable radical cation, [3 a][PF 6 ]
Journal of Labelled Compounds and Radiopharmaceuticals, 2013
The biodistribution of an N2 N2 &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;... more The biodistribution of an N2 N2 &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39; tetradentate gold(III) chelate, which is known to be cytotoxic towards a range of human cancer cell lines, was determined by a radiolabelled equivalent of the compound. The (198) Au-labelled gold(III) chelate of a bis(pyrrolide-imine) Schiff base ligand with a three-carbon di(azomethine) linkage was successfully synthesised with a high radiochemical yield of 73% and radiochemical purity of &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;gt;95%. The high energy γ-ray emitted by the (198) Au nucleus was used to follow the biodistribution of the compound in vivo in six male Sprague Dawley rats on a gamma camera. The log Po/w value of the (nat) Au analogue, -1.92(2), showed that the compound is hydrophilic and therefore likely to largely remain in the blood pool. This was confirmed by the biodistribution study, which showed 21% of the injected dose (ID) remained in the blood pool 4.5 h after injection. This decreased to 10.8% over a 24-h period. The activity measured in the lungs, 1.48%ID/g, remained relatively constant over a 24-h period suggesting that the complex had accumulated in the lungs in the form of particulates, and could not be cleared by the test subjects. The t½ for the heart and lungs was greater than 24 h. Excretion of the test compound is seemingly via the kidneys, but is slow with approximately 30% of the ID excreted within 24 h.
: A crystallographic and density functional theory investigation](https://attachments.academia-assets.com/49741782/thumbnails/1.jpg)
](Journal of Porphyrins and Phthalocyanines, 2004
The single crystal X-ray structure of [Co(TPP)(BzNH 2 ) 2 ](SCN), compound 2, where TPP = 5,10,15... more The single crystal X-ray structure of [Co(TPP)(BzNH 2 ) 2 ](SCN), compound 2, where TPP = 5,10,15,20-tetraphenylporphyrin dianion and BzNH 2 = benzylamine, reveals that the SCNion is hydrogen-bonded to one of the coordinated amino group hydrogen atoms via its sulfur atom. Furthermore, the N-H ... SCN interaction is balanced by a stronger N-H ... NCS hydrogen bonding interaction for the trans BzNH 2 ligand as a result of the multiple hydrogen bond accepting character of the thiocyanate ion. Analysis of the crystal packing shows that these two hydrogen bonds play a major role in fixing unusual orientations for the axial ligands relative to the porphyrin ring in this system. This, in turn, leads to the formation of a nonplanar porphyrin core conformation that is a mixture of ruffle-and saddle-type distortions. The intricate hydrogen bonding between the cations and anions in 2 results in an unusually long mean Co-N amine coordination distance of 2.033(4) Å, some 0.05 Å longer than previously observed for other bis(primary amine) complexes of Co(III) porphyrins with comparable porphyrin ligands. Density functional theory (DFT) calculations at the B3LYP/LACVP* level of theory have been used to gauge the perturbation of the electronic structure of the [Co(TPP)(BzNH 2 ) 2 ] + cation caused by the N-H ... SCN and N-H ... NCS hydrogen-bonded SCNions. The calculations show that partial mixing of the anion MOs with those of the porphyrin cation lead to changes in the electron populations of the 3d orbitals of up to 0.42 e as well as more nearly tetragonal electronic symmetry for the Co(III) ion as a result of adjustments of the relative energies of the MOs with predominantly 3d character.
Journal of Coordination Chemistry, 2013
ABSTRACT Herein we report the synthesis and characterization of trans-[RuII Cl2(PPh3)3] with pote... more ABSTRACT Herein we report the synthesis and characterization of trans-[RuII Cl2(PPh3)3] with potentially tridentate Schiff bases derived from 5,6-diamino-1,3-dimethyl uracil (H2ddd) and two 2-substituted aromatic aldehydes. In the diamagnetic ruthenium(II) complexes, trans-[RuCl(PPh3)2(Htdp)] (1) {H2tdp = 5-((thiophen-3-yl)methyleneamino)-6-amino-1,3-dimethyluracil} and trans-[RuCl(PPh3)2(Hsdp)] (2) {H2sdp = 5-(2-(methylthio)benzylideneamino)-6-amino-1,3-dimethyluracil}, the Schiff base ligands (i.e. Htdp and Hsdp) act as mono-anionic tridentate chelators. Upon reacting 5-(2-hydroxybenzylideneamino)-6-amino-1,3-dimethyluracil (H3hdp) with the metal precursor, the paramagnetic complex, trans-[RuIV Cl2(ddd)(PPh3)2] (3), was isolated, in which the bidentate dianionic ddd co-ligand was formed by hydrolysis. The metal complexes were fully characterized via multinuclear NMR-, IR-, and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. The redox properties were probed via cyclic voltammetry with all complexes exhibiting comparable electrochemical behavior with half-wave potentials (E ½) at 0.70 V (for 1), 0.725 V (for 2), and 0.68 V (for 3) versus Ag|AgCl, respectively. The presence of the paramagnetic metal center for 3 was confirmed by ESR spectroscopy.
Journal of The American Chemical Society, 1995
A new molecular mechanics (MM) force field model for six-coordinate low-spin imidazole and pyridi... more A new molecular mechanics (MM) force field model for six-coordinate low-spin imidazole and pyridine complexes of ferric porphyrins has been used with a modified version of the program MM2(87) to investigate the planar and ruffled conformations of [Fe(TMP)(L)# complexes, where L = a pyridine or imidazole derivative. All currently available X-ray structures in this class were used to gauge parametrization of the force field, including that of [Fe(TMP)( 1,2-Me~Im)z]C104, whose preparation, Mossbauer spectrum, and X-ray structure determination are described. [Fe(TMP)(1,2-Me2Im)~]C104 has the most ruffled core of any iron(1II) porphyrin described to date, with mean absolute core atom displacements Ca, c b , C,, and C,, of 0.41, 0.28, 0.72, and 0.42 A, respectively. The average Fe-N,, distance is also the shortest observed at 1.937 A. The MM-calculated and crystallographically observed structures of [Fe(TMP)(1,2-MezIm)2]+ both show that the porphyrin core is distorted from ideal DZd symmetry in response to anisotropic distribution of steric bulk in the axial ligands. Our calculations indicate that Du-ruffling of the porphyrin core hinges on a relative perpendicular orientation for the axial ligands, with the magnitude of distortion increasing with increasing ligand bulk (4(5)-MeHIm < pyridine < 1,2-MezIm < BzHIm < 2-MeBzHIm). The MM and crystallographic data therefore demonstrate that ligand-porphyrin nonbonded interactions are the primary determinant of core conformation in six-coordinate complexes. Furthermore, the meso-mesityl groups of [Fe(TMP)-(L)# derivatives exhibit slightly staggered minimum-energy orientations that become more staggered with increasing axial ligand bulk, providing direct evidence for nonbonded interactions between the ligands and the peripheral substituents. Since counterrotation of a trans pair of mesityl groups in Du-ruf [Fe(TMP)(2-MeBzHIm)z]+ only scarcely perturbed the minimum-energy orientations of the axial ligands, by inducing slight changes in the symmetry of the core distortion and direct intramolecular contact, ligand-peripheral group interactions control the finer aspects of molecular conformation. In contrast, nonbonded interactions between the peripheral aryl groups and the porphyrin core were the primary determinant of core conformation in four-coordinate Dwsad [Fe(meso-tetraarylporphyrin)]+ species. The calculated core distortion increased with increasing size of the meso-aryl substituents (phenyl < < 2,6dichlorophenyl < mesityl). Crystal data for [Fe(TMP)( 1,2-Me2Im)~]ClO4.0.65Cd-I~Cl*l .05Hz0: a = 14.958(24) A, b = 21.147(21) A, c = 20.897(32) A, p = 98.98(12)", space group P21/n, V = 6529 A3, Z = 4, T = 127 K, number of observed data = 8473, R1 = 0.072, Rz = 0.088.
Journal of The American Chemical Society, 1997
ABSTRACT
Acta crystallographica. Section C, Crystal structure communications, 2010
The crystal structures of two para-substituted aryl derivatives of pyridine-2-carboxamide, namely... more The crystal structures of two para-substituted aryl derivatives of pyridine-2-carboxamide, namely N-(4-fluorophenyl)pyridine-2-carboxamide, C(12)H(9)FN(2)O, (I), and N-(4-nitrophenyl)pyridine-2-carboxamide, C(12)H(9)N(3)O(3), (II), have been studied. Compound (I) exhibits unconventional aryl-carbonyl C-H...O and pyridine-fluorine C-H...F hydrogen bonding in two dimensions and well defined π-stacking involving pyridine rings in the third dimension. The conformation of (II) is more nearly planar than that of (I) and the intermolecular interactions comprise one-dimensional aryl-carbonyl C-H...O hydrogen bonds leading to a stepped or staircase-like progression of loosely π-stacked molecules. The close-packed layers of planar π-stacked molecules are related by inversion symmetry. Two alternating interplanar separations of 3.439 (1) and 3.476 (1) Å are observed in the crystal lattice and are consistent with a repetitive packing sequence, ABA'B'AB…, for the π-stacked inversion pair...
Acta Crystallographica Section C Crystal Structure Communications, 2012
The cation of the title complex salt, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]pro... more The cation of the title complex salt, chlorido{2,2-dimethyl-N-[(E)-1-(pyridin-2-yl)ethylidene]propane-1,3-diamine}platinum(II) tetrafluoridoborate, [PtCl(C(12)H(19)N(3))]BF(4), exhibits a nominally square-planar Pt(II) ion coordinated to a chloride ion [Pt-Cl = 2.3046 (9) Å] and three unique N-atom types, viz. pyridine, imine and amine, of the tridentate Schiff base ligand formed by the 1:1 condensation of 1-(pyridin-2-yl)ethanone and 2,2-dimethylpropane-1,3-diamine. The cations are π-stacked in inversion-related pairs (dimers), with a mean plane separation of 3.426 Å, an intradimer Pt···Pt separation of 5.0785 (6) Å and a lateral shift of 3.676 Å. The centroid (Cg) of the pyridine ring is positioned approximately over the Pt(II) ion of the neighbouring cation (Pt···Cg = 3.503 Å).
Inorganic chemistry, Jan 15, 2013
The structures, spectroscopy, and cytotoxicity of four novel nominally square-planar gold(III) ch... more The structures, spectroscopy, and cytotoxicity of four novel nominally square-planar gold(III) chelates 1-4 with the general formula cis-AuCl2(X), where the ligand X is an anionic bidentate pyridyl- or isoquinolylamido chelating agent, are described. The Au-N(amido), Au-N(pyridyl), and Au-N(isoquinolyl) distances are 2.002(9)-2.016(3), 2.01(1)-2.037(3), and 2.037(3) Å, respectively. Density functional theory simulations afforded accurate gold(III) coordination geometries for 1-4 (bond distances and angles to within 5% of the X-ray values), while accurate transition energies were limited to those calculated in the UV spectral region. The complexes had variable stability in dimethyl sulfoxide: compound 3 (relatively rigid) was indefinitely stable, compounds 1 and 2 (conformationally flexible) slowly demetalated over 30 days, and 4 (extensively aromatic) formed an insoluble precipitate after 10 days (72 h in an aqueous buffer). The isoquinolylamido derivative 4 was sufficiently cytotox...
Chemistry - A European Journal, 2014
A series of Group 7 Fischer carbene complexes, [Cp(CO) 2 Mn I = C(OEt)Ar] (Cp = cyclopentadienyl,... more A series of Group 7 Fischer carbene complexes, [Cp(CO) 2 Mn I = C(OEt)Ar] (Cp = cyclopentadienyl, Ar = Th = thienyl (1 a), Ar = Fu = furyl (2 a), Ar = Fc = ferrocenyl (3 a)) and biscarbene complexes, [Cp(CO) 2 Mn=C(OEt)ÀAr'À(OEt)C= Mn(CO) 2 Cp] (Ar' = Th' = 2,5-thienylene (1 b), Ar' = Fu' = 2,5furylene (2 b), Ar' = Fc' = 1,1'-ferrocendiyl (3 b)) was synthesized and characterized. Chemical oxidation of [Cp(CO) 2 Mn= C(OEt)Fc] (3 a) and isolation of the oxidised species [3 a][PF 6 ] possessing a Mn II centre proved possible below À30 8C in dichloromethane solution. The ESR spectrum of the transiently stable radical cation, [3 a][PF 6 ]
Journal of Labelled Compounds and Radiopharmaceuticals, 2013
The biodistribution of an N2 N2 &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;... more The biodistribution of an N2 N2 &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;#39; tetradentate gold(III) chelate, which is known to be cytotoxic towards a range of human cancer cell lines, was determined by a radiolabelled equivalent of the compound. The (198) Au-labelled gold(III) chelate of a bis(pyrrolide-imine) Schiff base ligand with a three-carbon di(azomethine) linkage was successfully synthesised with a high radiochemical yield of 73% and radiochemical purity of &amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;amp;gt;95%. The high energy γ-ray emitted by the (198) Au nucleus was used to follow the biodistribution of the compound in vivo in six male Sprague Dawley rats on a gamma camera. The log Po/w value of the (nat) Au analogue, -1.92(2), showed that the compound is hydrophilic and therefore likely to largely remain in the blood pool. This was confirmed by the biodistribution study, which showed 21% of the injected dose (ID) remained in the blood pool 4.5 h after injection. This decreased to 10.8% over a 24-h period. The activity measured in the lungs, 1.48%ID/g, remained relatively constant over a 24-h period suggesting that the complex had accumulated in the lungs in the form of particulates, and could not be cleared by the test subjects. The t½ for the heart and lungs was greater than 24 h. Excretion of the test compound is seemingly via the kidneys, but is slow with approximately 30% of the ID excreted within 24 h.
Journal of Porphyrins and Phthalocyanines, 2004
The single crystal X-ray structure of [Co(TPP)(BzNH 2 ) 2 ](SCN), compound 2, where TPP = 5,10,15... more The single crystal X-ray structure of [Co(TPP)(BzNH 2 ) 2 ](SCN), compound 2, where TPP = 5,10,15,20-tetraphenylporphyrin dianion and BzNH 2 = benzylamine, reveals that the SCNion is hydrogen-bonded to one of the coordinated amino group hydrogen atoms via its sulfur atom. Furthermore, the N-H ... SCN interaction is balanced by a stronger N-H ... NCS hydrogen bonding interaction for the trans BzNH 2 ligand as a result of the multiple hydrogen bond accepting character of the thiocyanate ion. Analysis of the crystal packing shows that these two hydrogen bonds play a major role in fixing unusual orientations for the axial ligands relative to the porphyrin ring in this system. This, in turn, leads to the formation of a nonplanar porphyrin core conformation that is a mixture of ruffle-and saddle-type distortions. The intricate hydrogen bonding between the cations and anions in 2 results in an unusually long mean Co-N amine coordination distance of 2.033(4) Å, some 0.05 Å longer than previously observed for other bis(primary amine) complexes of Co(III) porphyrins with comparable porphyrin ligands. Density functional theory (DFT) calculations at the B3LYP/LACVP* level of theory have been used to gauge the perturbation of the electronic structure of the [Co(TPP)(BzNH 2 ) 2 ] + cation caused by the N-H ... SCN and N-H ... NCS hydrogen-bonded SCNions. The calculations show that partial mixing of the anion MOs with those of the porphyrin cation lead to changes in the electron populations of the 3d orbitals of up to 0.42 e as well as more nearly tetragonal electronic symmetry for the Co(III) ion as a result of adjustments of the relative energies of the MOs with predominantly 3d character.
Journal of Coordination Chemistry, 2013
ABSTRACT Herein we report the synthesis and characterization of trans-[RuII Cl2(PPh3)3] with pote... more ABSTRACT Herein we report the synthesis and characterization of trans-[RuII Cl2(PPh3)3] with potentially tridentate Schiff bases derived from 5,6-diamino-1,3-dimethyl uracil (H2ddd) and two 2-substituted aromatic aldehydes. In the diamagnetic ruthenium(II) complexes, trans-[RuCl(PPh3)2(Htdp)] (1) {H2tdp = 5-((thiophen-3-yl)methyleneamino)-6-amino-1,3-dimethyluracil} and trans-[RuCl(PPh3)2(Hsdp)] (2) {H2sdp = 5-(2-(methylthio)benzylideneamino)-6-amino-1,3-dimethyluracil}, the Schiff base ligands (i.e. Htdp and Hsdp) act as mono-anionic tridentate chelators. Upon reacting 5-(2-hydroxybenzylideneamino)-6-amino-1,3-dimethyluracil (H3hdp) with the metal precursor, the paramagnetic complex, trans-[RuIV Cl2(ddd)(PPh3)2] (3), was isolated, in which the bidentate dianionic ddd co-ligand was formed by hydrolysis. The metal complexes were fully characterized via multinuclear NMR-, IR-, and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. The redox properties were probed via cyclic voltammetry with all complexes exhibiting comparable electrochemical behavior with half-wave potentials (E ½) at 0.70 V (for 1), 0.725 V (for 2), and 0.68 V (for 3) versus Ag|AgCl, respectively. The presence of the paramagnetic metal center for 3 was confirmed by ESR spectroscopy.