2002
DOI: 10.1002/ejic.200390026
|View full text |Cite
|
Sign up to set email alerts
|

Elucidation of the Solution Structures of Transition Metal Complex Ion Pairs by NOE NMR Experiments

Abstract: Our results from structural investigations of transition metal complex ion pairs in solution by homonuclear and heteronuclear 1D‐ and 2D‐NOE NMR spectroscopy are reviewed. Both model (A) and catalytically active (B) complexes have been taken into account; their general formulas are: trans‐[ML2(N,X)(Y)(Z)]+A− (A) {M = FeII, RuII and OsII, L = PMe3, Y = CO, Z = COMe, A− = BPh3R−, CF3SO3−, BF4−, PF6− and B[3,5‐(CF3)2C6H3]4−; M = IrIII, L = PR3, Y = Z = H and A− = BPh4−, CF3SO3−, BF4−, PF6−} and [M′(N,X)(R,olefin)… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
4

Citation Types

6
101
0

Year Published

2005
2005
2016
2016

Publication Types

Select...
7
1
1

Relationship

2
7

Authors

Journals

citations
Cited by 111 publications
(107 citation statements)
references
References 65 publications
6
101
0
Order By: Relevance
“…2 The latter are extremely important and critically affect the establishment of supramolecular inorganic assemblies and the reactivity of coordination compounds and organometallics, often used as catalysts for reaction of industrial interest. 3 Particularly, the combination of NOE (Nuclear Overhauser Effect) 4 and diffusion NMR techniques 5 emerged as an extremely powerful tool for investigating the relative orientation (NOE) and the level of aggregation (diffusion) of non-covalently bonded inorganic systems. 6 the industrially relevant methylaluminoxane (MAO); 3) the combination of ion pairing and H-bonding in tuning the reactivity of gold(I) cationic catalysts; 4) non-covalent interactions in halogen-bonded adducts; 5) the supramolecular structure of intermolecular Frustrated Lewis Pairs.…”
Section: Introductionmentioning
confidence: 99%
“…2 The latter are extremely important and critically affect the establishment of supramolecular inorganic assemblies and the reactivity of coordination compounds and organometallics, often used as catalysts for reaction of industrial interest. 3 Particularly, the combination of NOE (Nuclear Overhauser Effect) 4 and diffusion NMR techniques 5 emerged as an extremely powerful tool for investigating the relative orientation (NOE) and the level of aggregation (diffusion) of non-covalently bonded inorganic systems. 6 the industrially relevant methylaluminoxane (MAO); 3) the combination of ion pairing and H-bonding in tuning the reactivity of gold(I) cationic catalysts; 4) non-covalent interactions in halogen-bonded adducts; 5) the supramolecular structure of intermolecular Frustrated Lewis Pairs.…”
Section: Introductionmentioning
confidence: 99%
“…[4] As the development of new catalysts generally benefits from ad eeper understanding of the reaction mechanism, modern NMR spectroscopic techniques such as pulsed gradient spin echo (PGSE) and NOE experiments as well as electronic circular dichroism (ECD) spectroscopy have been used to probe the stereochemical communication within ion pairs. [4,5] However,w hile NMR spectroscopy in itself is not sensitive to chirality but, for instance,t ot he formation of diastereomers,electronic transitions observed in ECD usually feature quite broad absorbance bands.T his may complicate the interpretation of the spectra, as,f or instance,b ands of cations and anions featuring similar chromophors can overlap,s olvent absorbance might cover important transitions, and the prediction of ECD band intensities and signs can be challenging.[6] Clearly,additional methods and techniques are required to investigate chiral ion pairing systems.Vibrational circular dichroism (VCD) spectroscopy is the chiroptical version of infrared spectroscopy and as such measures the very small difference in the absorbance of lefthanded and right-handed circularly polarized infrared light during av ibrational transition. …”
mentioning
confidence: 99%
“…NOE experiments allow the relative anion-cation orientation within the ion pair to be determined. [9] Diffusion experiments can be used to evaluate the average hydrodynamic size of the aggregates including the ions. Consequently, from diffusion measurements, it is possible to understand 6 , Im= imidazole, X = PF 6 ) has been isolated and characterized by single-crystal XRD.…”
Section: Introductionmentioning
confidence: 99%
“…[3] Rather surprisingly, the ion pairing phenomenon has not been investigated in organometallic dendrimers and very rarely in dendrimers in general, [4] even though it is well known that ion pairing causes remarkable changes in the activity and regio-and stereoselectivity of organometallic compounds. [5] Diffusion [6,7] and NOE [8,9] (nuclear Overhauser effect) NMR experiments are powerful tools for investigating ion pairing and self-aggregation. [10][11][12][13][14] They have been used to elucidate the interionic structure of many organometallic salts.…”
Section: Introductionmentioning
confidence: 99%