Synthesis, structure and EPR spectroscopy of a vanadium(IV)–amide metallacyclic complex

Cornman, Charles R.; Zovinka, Edward P.; Boyajian, Yvette D.; Olmstead, Marilyn M.; Noll, Bruce C.

doi:10.1016/s0020-1693(98)00261-8

Cited by 12 publications

(5 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compound 2 ·2CHCl 3 represents a rare example, 14b, the first known for vanadium, of a deprotonated amide coordinated via oxygen and not nitrogen. Ab initio calculations have shown that the structure adopted by 2 ·2CHCl 3 is a result of a fine balance of the ligand deformation energy, the relative strength of each coordination mode, and steric hindrance.…”

Section: Discussionmentioning

confidence: 99%

“…A literature survey, for the diamidate ligand H 2 bpb, revealed that in almost all the crystallographically characterized H 2 bpb−metal compounds, the ligand acts as a dianionic planar bis[ N -amidate- N -pyridine] chelator . To this trend, there are only two exceptions . Metal−bpb 2- compounds have been used as epoxidation 13d, or hydroxylation catalysts.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)

et al. 2000

View full text Add to dashboard Cite

Novel vanadium(III) and oxovanadium(IV) compounds with the diamidate ligand 1,2-bis(2-pyridinecarboxamide)benzene (H2bpb) were synthesized and structurally characterized. H2bpb is capable of binding to vanadium in either its anionic (dianionic-monoanionic) or its neutral form, resulting in complexes of various geometries and stoichiometries. The dianionic form (bpb2-), in NHEt3(trans-[VCl2(bpb)]) (1) and [VO(bpb)(H2O)]05dmso036CH3OH013H2O (6x05dmsox036CH3OHx013H2O), acts as a planar tetradentate bis[N-amidate-N-pyridine] equatorial ligand. The monoanionic form (Hbpb-) behaves as an (Npy,Oam) or (Npy,Nam) chelator in [V(Hbpb)3]2CHCl3 (22CHCl3) as well as a mu 2-bridging-eta 4-(Npy,Oam-Npy,Nam) in [VOCl(Hbpb)](2)x2CH3NO2 (3x2CH3NO2), while the neutral H2bpb behaves as a mu 2-bridging-eta 4-bis(Npy,Oam) in [VOCl(H2bpb)](2)x104CH3OHx123thfx074H2O (4x104CH3OH123thf074H2O). Compound 4x104CH3OHx123thfx074H2O crystallizes in the triclinic system P1, with (at 25 degrees C) a = 9140(2) A, b = 11058(2) A, c = 14175(2) A, alpha = 99013(5) degrees, beta = 104728(7) degrees, gamma = 102992(7) degrees, V = 13149(4) A3, Z = 1, while compound 605dmso036CH3OH013H2O crystallizes in the monoclinic space group P2(1)/n with (at 25 degrees C) a = 11054(5) A, b = 11407(5) A, c = 16964(7) A, beta = 932(1) degrees, V = 2136(2) A3, Z = 4. Variable temperature magnetic susceptibility studies of the dimeric compounds 3x2CH3NO2 and 4x104CH3OH show g values for the V(IV) centers that are slightly smaller than 20 (as expected for d1 ions) and indicate small antiferromagnetic coupling between the two vanadium(IV) centers. Ab initio calculations were also carried out, providing results concerning the effect of the relative strength and the deformation energy involved in the eta 2-(Npy,Nam) and eta 2-(Npy,Oam) bonding modes in the ligation of Hbpb- to vanadium.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)

et al. 2000

View full text Add to dashboard Cite

show abstract

“…Bis(pyridine-amide) and bis(quinoline-amide) derivatives comprise a large group of organic compounds that are ideal for the mono-or dinuclear chelation of metal ions (Tsuboyama et al, 1984;Chan et al, 1998;Cornman et al, 1999), as well as the formation of coordination polymers (Kajikawa et al, 1998;van der Horst et al, 2008). The basic structural features of these compounds allow them to function as multidentate N,N 0 -donor ligands, or as mixed N,O-donor ligands in situations where the carbonyl O atoms are used for binding.…”

Section: Commentmentioning

confidence: 99%

Amide hydrogen bonding: control of the molecular and extended structures of two symmetrical pyridine-2-carboxamide derivatives

Munro

Wilson

2010

Acta Crystallogr C

View full text Add to dashboard Cite

The crystal structures of two symmetrical pyridine-2-carboxamides, namely N,N'-(propane-1,3-diyl)bis(pyridine-2-carboxamide), C(15)H(16)N(4)O(2), (I), and N,N'-(butane-1,4-diyl)bis(pyridine-2-carboxamide), C(16)H(18)N(4)O(2), (II), exhibit extended hydrogen-bonded sequences involving their amide groups. In (I), conventional bifurcated amide-carbonyl (N-H)...O hydrogen bonding favours the formation of one-dimensional chains, the axes of which run parallel to [001]. Unconventional bifurcated pyridine-carbonyl C-H...O hydrogen bonding links adjacent one-dimensional chains to form a `porous' three-dimensional lattice with interconnected, yet unfilled, voids of 60.6 (2) Å(3) which combine into channels that run parallel to, and include, [001]. 4% of the unit-cell volume of (I) is vacant. Compound (II) adopts a Z-shaped conformation with inversion symmetry, and exhibits an extended structure comprising one-dimensional hydrogen-bonded chains along [100] in which individual molecules are linked by complementary pairs of amide N-H...O hydrogen bonds. These hydrogen-bonded chains interlock via π-π interactions between pyridine rings of neighbouring molecules to form sheets parallel with (010); each sheet is one Z-shaped molecule thick and separated from the next sheet by the b-axis dimension [7.2734 (4) Å].

show abstract

“…Furthermore, carboxamide derivatives are ideal molecules for chelating metal ions since deprotonation of the amide N-H group affords a powerfuldonor group. Coupled with additional functional groups based on N-, O-or S-donor atoms, polydentate carboxamides may be synthesized with variable arrays of metal-binding sites (Zhang et al, 2002;Dasgupta et al, 2008;Cornman et al, 1999;Jiang et al, 2004).…”

Section: Commentmentioning

confidence: 99%

Unconventional hydrogen bonding and π-stacking in two substituted pyridine carboxamides

Wilson

Munro

2010

Acta Crystallogr C Cryst Struct Commun

View full text Add to dashboard Cite

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 pairs of (II).

show abstract

Synthesis, structure and EPR spectroscopy of a vanadium(IV)–amide metallacyclic complex

Cited by 12 publications

References 13 publications

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)

Amide hydrogen bonding: control of the molecular and extended structures of two symmetrical pyridine-2-carboxamide derivatives

Unconventional hydrogen bonding and π-stacking in two substituted pyridine carboxamides

Contact Info

Product

Resources

About

Synthesis, structure and EPR spectroscopy of a vanadium(IV)–amide metallacyclic complex

Cited by 12 publications

References 13 publications

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H2bpb)

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H2bpb)

Amide hydrogen bonding: control of the molecular and extended structures of two symmetrical pyridine-2-carboxamide derivatives

Unconventional hydrogen bonding and π-stacking in two substituted pyridine carboxamides

Contact Info

Product

Resources

About

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)

Model Investigations of Vanadium−Protein Interactions: Novel Vanadium(III) and Oxovanadium(IV) Compounds with the Diamidate Ligand 1,2-Bis(2-pyridinecarboxamide)benzene (H₂bpb)