Fluxional Processes in Diamagnetic and Paramagnetic Allyl Dicarbonyl and 2-Methylallyl Dicarbonyl Molybdenum Histidinato Complexes as Revealed by Spectroscopic Data and Density Functional Calculations

Staveren, Dave R. van; Bill, Eckhard; Bothe, Eberhard; Bühl, Michæl; Weyhermüller, Thomas; Metzler‐Nolte, Nils

doi:10.1002/1521-3765(20020402)8:7<1649::aid-chem1649>3.0.co;2-u

“…The bpa ligand, on the other hand, is readily substituted with a carboxylic acid group. [8,9] In this work, we have demonstrated that fac-Mo(CO) 3 derivatives of the bpa ligand are well suited for the labelling of biomolecules. [55Ϫ60] Secondly, the bioconjugate must be stable in water and air for quite some time.…”

Section: Discussionmentioning

confidence: 99%

Spectroscopic Properties, Electrochemistry, and Reactivity of Mo0, MoI, and MoII Complexes with the [Mo(bpa)(CO)3] Unit [bpa = bis(2-picolyl)amine] and Their Application for the Labelling of Peptides

Staveren¹,

Bothe²,

Weyhermüller³

et al. 2002

Eur. J. Inorg. Chem.

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Keywords: Amino acids / Bioinorganic chemistry / Carbonyl ligands / Molybdenum / Spectro-electrochemistryThe synthesis of the complexes [Mo(bpa)(CO) 3 ] (1) and [Mo(Bz-bpa)(CO) 3 ] (2) [bpa = bis(2-picolyl)amine; Bz-bpa = N-benzylbis(2-picolyl)amine] is described. These compounds have been characterized by spectroscopic techniques including multinuclear NMR spectroscopy ( 1 H, 13 C, and 95 Mo), and also by X-ray crystallography. Complexes 1 and 2 underwent reversible one-electron oxidations in acetonitrile and dichloromethane with Bu 4 NPF 6 as supporting electrolyte to yield the 17-electron organometallic compounds 1 + and 2 + . With Bu 4 NBr as supporting electrolyte in dichloromethane, on the other hand, 1 and 2 underwent electrochemically irreversible two-electron oxidations, resulting in the formation of [Mo(bpa)(CO) 3 Br] + and [Mo(Bz-bpa)(CO) 3 Br] + . Infrared spectra and electronic spectra of these oxidized species were recorded in spectro-electrochemical studies. The electrochemical behaviour and the infrared spectroscopic data of 1, 2, and their oxidized derivatives are compared in detail with those of analogous tricarbonylmolybdenum complexes with [a]

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“…We were then able to show that isolobal replacement of the cyclopentadienyl ligand with histidinate resulted in complexes of the general type [Mo(His)(allyl)(CO) 2 ], with very favourable electrochemical properties and much increased stability towards air even in solution. [8,9] In this work, we have demonstrated that fac-Mo(CO) 3 derivatives of the bpa ligand are well suited for the labelling of biomolecules. On comparing benzyl-substituted [Mo(Bzbpa)(CO) 3 ] (2) to the bioconjugates 8 we note that there is very little influence of the attached biomolecule on the spectroscopic properties of the metal complex.…”

Section: Discussionmentioning

confidence: 99%

Spectroscopic Properties, Electrochemistry, and Reactivity of Mo0, MoI, and MoII Complexes with the [Mo(bpa)(CO)3] Unit [bpa = bis(2-picolyl)amine] and Their Application for the Labelling of Peptides

Staveren

¹

,

Bothe

²

,

Weyhermüller

³

et al. 2002

Eur. J. Inorg. Chem.

Self Cite

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Keywords: Amino acids / Bioinorganic chemistry / Carbonyl ligands / Molybdenum / Spectro-electrochemistryThe synthesis of the complexes [Mo(bpa)(CO) 3 ] (1) and [Mo(Bz-bpa)(CO) 3 ] (2) [bpa = bis(2-picolyl)amine; Bz-bpa = N-benzylbis(2-picolyl)amine] is described. These compounds have been characterized by spectroscopic techniques including multinuclear NMR spectroscopy ( 1 H, 13 C, and 95 Mo), and also by X-ray crystallography. Complexes 1 and 2 underwent reversible one-electron oxidations in acetonitrile and dichloromethane with Bu 4 NPF 6 as supporting electrolyte to yield the 17-electron organometallic compounds 1 + and 2 + . With Bu 4 NBr as supporting electrolyte in dichloromethane, on the other hand, 1 and 2 underwent electrochemically irreversible two-electron oxidations, resulting in the formation of [Mo(bpa)(CO) 3 Br] + and [Mo(Bz-bpa)(CO) 3 Br] + . Infrared spectra and electronic spectra of these oxidized species were recorded in spectro-electrochemical studies. The electrochemical behaviour and the infrared spectroscopic data of 1, 2, and their oxidized derivatives are compared in detail with those of analogous tricarbonylmolybdenum complexes with

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“…The lower activation energy of methallyl respect to allyl complexes in the system [Mo(g 3 -CH 2 C(R)HCH 2 )X(CO) 2 L 2 ] has been already reported [25].…”

Section: Characterization In Solutionmentioning

confidence: 99%

fac-Acetato-bis(pyrazole) complexes: A systematic study on intra- and intermolecular hydrogen bonds

Arroyo

¹

,

García-de-Prada

²

,

García-Martín

³

et al. 2009

Journal of Organometallic Chemistry

8

1

0

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Fluxional Processes in Diamagnetic and Paramagnetic Allyl Dicarbonyl and 2-Methylallyl Dicarbonyl Molybdenum Histidinato Complexes as Revealed by Spectroscopic Data and Density Functional Calculations

Cited by 33 publications

References 68 publications

Spectroscopic Properties, Electrochemistry, and Reactivity of Mo0, MoI, and MoII Complexes with the [Mo(bpa)(CO)3] Unit [bpa = bis(2-picolyl)amine] and Their Application for the Labelling of Peptides

Spectroscopic Properties, Electrochemistry, and Reactivity of Mo0, MoI, and MoII Complexes with the [Mo(bpa)(CO)3] Unit [bpa = bis(2-picolyl)amine] and Their Application for the Labelling of Peptides

Spectroscopic Properties, Electrochemistry, and Reactivity of Mo0, MoI, and MoII Complexes with the [Mo(bpa)(CO)3] Unit [bpa = bis(2-picolyl)amine] and Their Application for the Labelling of Peptides

fac-Acetato-bis(pyrazole) complexes: A systematic study on intra- and intermolecular hydrogen bonds

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