Application of <sup>1</sup>H-NOESY NMR Spectroscopy to the Investigation of Ion Pair Solution Structures of Organometallic Complexes by the Detection of Interionic Contacts

Bellachioma, Gianfranco; Cardaci, Giuseppe; Macchioni, Alceo; Reichenbach, and Gustavo; Terenzi, Silvia

doi:10.1021/om9605645

Cited by 58 publications

(34 citation statements)

References 22 publications

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“…Clearly, the choice of solvent and anion can have an effect on salt aggregation, a subject that is sometimes overlooked. In an extensive study over several decades, Macchioni and co-workers [13,47,48,[93][94][95][96][97][98][99][100][101][102][103][104][105][106][107][108][109] have shown that, even at modest concentration, as well as in relatively polar alcohol solutions, various salts aggregate. A useful example involves the self-aggregation tendency of the long chain ammonium salts, [N(CH 3 ) 2 (C 18 H 37 ) 2 ]X, X À = BF 4 À , PF 6 À , CF 3 SO 3 À , NTf 2 À , BPh 4 À , B(p-Tol) 4 À , BArF À and B(C 6 F 5 ) 4 À , 9, to form ion quadruples (IQs) and higher aggregates in deuterated benzene.…”

Section: Values Are ×10mentioning

confidence: 99%

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Pregosin

2016

Magnetic Reson in Chemistry

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Section: Values Are ×10mentioning

confidence: 99%

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Pregosin

2016

Magnetic Reson in Chemistry

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“…Moreover, it is not possible to use conductivity data, even qualitatively, to estimate the extent of ion pairing. The diffusion data from the NMR experiments, when taken together with (NOESY or HOESY) Overhauser studies, which allow one to place the anion in three-dimensional space relative to the cation [110][111][112][113][114][115][116][117][118][119][120][121][122][123], frequently determine the structural details for the ion pair. This is yet another advantage of this NMR approach to ion pairing.…”

Section: Ion Pairingmentioning

confidence: 99%

Ion pairing using PGSE diffusion methods

Pregosin

2006

Progress in Nuclear Magnetic Resonance Spectroscopy

141

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“…Equally interesting results arise from studies on charged complexes with relatively large anions. On the basis of data collected by the PGSE methodology, Zuccaccia et al [29] recently suggested that the tetraphenyl borate cationic Ru-complexes of pyrazolylmethane 42 [51] (and an analogous pyrazolylborate derivative) can exist as tight ion pairs in dilute CHCl 3 solution. Clearly, in CD 2 Cl 2 , the cation and anion are diffusing separately.…”

Section: Ionicmentioning

confidence: 99%

Applications of Pulsed-Gradient Spin-Echo (PGSE) Diffusion Measurements in Organometallic Chemistry

Valentini¹,

Rüegger²,

Pregosin³

2001

HCA

123

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With personal pleasure, we dedicate this Perspective to the memory of Luigi M. Venanzi, who, apart from his many scientific contributions, was a major promotor of NMR spectroscopy within the Swiss and international Inorganic Chemistry communities.Diffusion data from pulsed-field gradient spin-echo (PGSE) methods are shown to be qualitatively useful in the investigation of problems involving unknown molecular aggregation and/or the nature of inter-ionic interactions in metal complexes. For charged species possessing anions such as PF À 6 , BF À 4 , CF 3 SO À 3 or BArF À , both 19 F-and 1 H-PGSE methods offer a valid alternative and, sometimes, unique view of gross and subtle solution molecular structure and dynamics. Problems associated with solvents, concentration, and reproducibility are discussed.1. Introduction. ± Although organometallic chemistry (and especially homogeneous catalysis) continues to move from strength to strength [1 ± 5], the applications of modern NMR methods in these areas have lagged somewhat behind. Slowly, but surely, three-dimensional structures are being solved with NOE-and ROE-NMR methods [6 ± 9]; nevertheless, there are areas, e.g., determining molecular size, aggregation, and/ or the nature of interionic interactions, where NMR spectroscopic possibilities have not been sufficiently explored.A promising NMR method involves the use of pulsed-field gradient spin-echo (PGSE) experiments [10], which can measure the diffusion coefficients of molecules and thus provide information on particle size. PGSE Methods were introduced in 1965 by Stejskal and co-workers [11] [12] and, since then, have been widely used. In the 1970s, this approach was used to determine diffusion coefficients of organic molecules [13]. In the following decade, variants of this technique have been applied to problems in polymer chemistry [14]. Recently, diffusion data on dendrimers [15 ± 20] and peptides [21 ± 24] as well as on molecules in various environments, e.g., in porous silica [25], and zeolites [26], have been obtained. However, there are very few applications of PGSE methods in coordination and/or organometallic chemistry [27 ± 35].In an interesting and recent application, Beck et al. [27] have studied the polymerization catalyst precursors 1 ± 5. Their results prompted the authors to suggest that these zirconium complexes can exist as ion-quadruples in the presence of a boronbased cocatalyst. In their construction of novel Pt-molecules, Olenyuk et al. [28] employed diffusion data to support a self-assembled dodecahedron structure of the product of the reaction shown in the Scheme. In a bio-inorganic application, Gorman et al.[15] estimated the hydrodynamic radii of the iron-sulphur based dendrimers, abbreviated below, using PGSE studies. These three examples are impressive as much for their scarcity as for their elegance.

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Application of ¹H-NOESY NMR Spectroscopy to the Investigation of Ion Pair Solution Structures of Organometallic Complexes by the Detection of Interionic Contacts

Cited by 58 publications

References 22 publications

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Ion pairing using PGSE diffusion methods

Applications of Pulsed-Gradient Spin-Echo (PGSE) Diffusion Measurements in Organometallic Chemistry

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Application of 1H-NOESY NMR Spectroscopy to the Investigation of Ion Pair Solution Structures of Organometallic Complexes by the Detection of Interionic Contacts

Cited by 58 publications

References 22 publications

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Applications of NMR diffusion methods with emphasis on ion pairing in inorganic chemistry: a mini‐review

Ion pairing using PGSE diffusion methods

Applications of Pulsed-Gradient Spin-Echo (PGSE) Diffusion Measurements in Organometallic Chemistry

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Application of ¹H-NOESY NMR Spectroscopy to the Investigation of Ion Pair Solution Structures of Organometallic Complexes by the Detection of Interionic Contacts