NMR <i>J</i>‐Coupling Constants in Cisplatin Derivatives Studied by Molecular Dynamics and Relativistic DFT

Sutter, Kiplangat; Truflandier, Lionel A.; Autschbach, Jochen

doi:10.1002/cphc.201000997

Cited by 29 publications

(36 citation statements)

References 61 publications

(83 reference statements)

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“…In addition, an axial Cl − ligand appears to weaken an equatorial PtNH 3 bond to a greater extent than an axial OH − . It can be anticipated that a combination of recent encouraging progress in the calculation of NMR spectroscopic chemical shifts38 and scalar coupling constants39 for Pt‐containing compounds in combination with the experimental data reported here, will lead to further insights into the bonding and reactivity of both Pt II and Pt IV complexes.…”

Section: Resultsmentioning

confidence: 73%

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Zhao

Lei

Dong

et al. 2013

Chemistry A European J

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The reactions of dialumane [L(thf)Al-Al(thf)L] (1, L=[{(2,6-iPr2C6H3)NC(Me)}2](2-)) with stilbene and styrene afforded the oxidation/insertion products [L(thf)Al(CH(Ph)-CH(Ph))AlL] (2) and [L(thf)Al(CH(Ph)-CH2)Al(thf)L] (3), respectively. In the presence of Na metal, precursor 1 reacted with butadienes, possibly through the reduced "dialumene" or the "carbene-like" :AlL species, to yield aluminacyclopentenes [LAl(CH2C(Me)=C(Me)CH2)Na]n (4 a) and [Na(dme)3][LAl(CH2C(Me)=CHCH2)] (4 b, dme=dimethoxyethane) as [1+4] cycloaddition products, as well as the [2+4] cycloaddition product 1,6-dialumina-3,8-cyclodecadiene, [{Na(dme)}2][LAl(CH2C(Me)=C(Me)CH2)2AlL] (5). The possible mechanisms of the cycloaddition reactions were studied by using DFT computations.

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Section: Resultsmentioning

confidence: 73%

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Zhao

Lei

Dong

et al. 2013

Chemistry A European J

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“…It can be anticipated that a combination of recent encouraging progress in the calculation of NMR spectroscopic chemical shifts [38] and scalar coupling constants [39] for Pt-containing compounds in Caution! No problems were encountered during this work, however, heavy metal azides can be shock-sensitive detonators, therefore it is essential that they are handled with care.…”

Section: Axial Bound CLmentioning

confidence: 99%

Probing Platinum Azido Complexes by ¹⁴N and ¹⁵N NMR Spectroscopy

Farrer

Gierth

Sadler

2011

Chemistry A European J

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Metal azido complexes are of general interest due to their high energetic properties, and platinum azido complexes in particular because of their potential as photoactivatable anticancer prodrugs. However, azido ligands are difficult to probe by NMR spectroscopy due to the quadrupolar nature of (14)N and the lack of scalar (1)H coupling to enhance the sensitivity of the less abundant (15)N by using polarisation transfer. In this work, we report (14)N and (15)N NMR spectroscopic studies of cis,trans,cis-[Pt(N(3))(2)(OH)(2)(NH(3))] (1) and trans,trans,trans-[Pt(N(3))(2)(OH)(2)(X)(Y)], where X=Y=NH(3) (2); X=NH(3), Y=py (3) (py=pyridine); X=Y=py (4); and selected Pt(II) precursors. These studies provide the first (15)N NMR data for azido groups in coordination complexes. We discuss one- and three-bond J((15)N,(195)Pt) couplings for azido and am(m)ine ligands. The (14)N(α) (coordinated azido nitrogen) signal in the Pt(IV) azido complexes is extremely broad (W(1/2)≈2124 Hz for 4) in comparison to other metal azido complexes, attributable to a highly asymmetrical electric field gradient at the (14)N(α) atom. Through the use of anti-ringing pulse sequences, the (14)N NMR spectra, which show resolution of the broad (14)N(α) peak, were obtained rapidly (e.g., 1.5 h for 10 mM 4). The linewidths of the (14)N(α) signals correlate with the viscosity of the solvent. For (15) N-enriched samples, it is possible to detect azido (15)N resonances directly, which will allow photoreactions to be followed by 1D (15)N NMR spectroscopy. The T(1) relaxation times for 3 and 4 were in the range 5.7-120 s for (15)N, and 0.9-11.3 ms for (14)N. Analysis of the (1)J((15)N,(195)Pt) coupling constants suggests that an azido ligand has a moderately strong trans influence in octahedral Pt(IV) complexes, within the series 2-pic

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“…A good example are platinum derivatives. In one of the papers, the J-coupling constants of cisplatin derivatives were investigated with the aiMD combined with DFT-NMR calculations [ 46 ]. Both the explicit and implicit solvation models were used.…”

Section: Summary Of the Chosen Studies Applying Both Aimd And Nmr Parameters Calculationmentioning

confidence: 99%

A Review on Combination of Ab Initio Molecular Dynamics and NMR Parameters Calculations

Mazurek

Szeleszczuk

Pisklak

2021

IJMS

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This review focuses on a combination of ab initio molecular dynamics (aiMD) and NMR parameters calculations using quantum mechanical methods. The advantages of such an approach in comparison to the commonly applied computations for the structures optimized at 0 K are presented. This article was designed as a convenient overview of the applied parameters such as the aiMD type, DFT functional, time step, or total simulation time, as well as examples of previously studied systems. From the analysis of the published works describing the applications of such combinations, it was concluded that including fast, small-amplitude motions through aiMD has a noticeable effect on the accuracy of NMR parameters calculations.

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NMR J‐Coupling Constants in Cisplatin Derivatives Studied by Molecular Dynamics and Relativistic DFT

Cited by 29 publications

References 61 publications

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Probing Platinum Azido Complexes by ¹⁴N and ¹⁵N NMR Spectroscopy

A Review on Combination of Ab Initio Molecular Dynamics and NMR Parameters Calculations

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NMR J‐Coupling Constants in Cisplatin Derivatives Studied by Molecular Dynamics and Relativistic DFT

Cited by 29 publications

References 61 publications

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Reactivity of Dialumane and “Dialumene” Compounds toward Alkenes

Probing Platinum Azido Complexes by 14N and 15N NMR Spectroscopy

A Review on Combination of Ab Initio Molecular Dynamics and NMR Parameters Calculations

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Product

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Probing Platinum Azido Complexes by ¹⁴N and ¹⁵N NMR Spectroscopy