Solid-state NMR Spectroscopy in Organometallic Chemistry

Wasylishen, Roderick E.; Bernard, Guy M.

doi:10.1016/b0-08-045047-4/00019-4

Cited by 6 publications

(2 citation statements)

References 250 publications

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“…Alternatively, some investigators have turned to nuclear quadrupole resonance (NQR) experiments to investigate Cu(I) complexes; , however, these experiments only provide the NQR frequency ν NQR = ν Q (1 + η Q 2 /3) 1/2 , where, for spin-3/2 nuclei such as 63/65 Cu, ν Q = 0.5 C Q , and η Q defines the asymmetry in the EFG tensor. However, because only one transition is observed in NQR measurements of S = 3/2 nuclei of powder samples, η Q or ν Q cannot be determined independently. , Furthermore, information about the copper magnetic shielding tensor is not obtained, nor, in the case of powder samples, does the technique yield information about the EFG tensor orientation.…”

Section: Introductionmentioning

confidence: 99%

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Tan

Bernard

et al. 2015

J. Phys. Chem. A

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The results of a solid-state (63/65)Cu and (31)P NMR investigation of several copper(I) complexes with functionalized 3-(2'-pyridyl)-1,2,4-triazole and phosphine ligands that have shown potential in the preparation of photoluminescent devices are reported. For each complex studied, distinct NMR parameters, with moderate (63)Cu nuclear quadrupolar coupling constant (CQ) values ranging from -17.2 to -23.7 MHz, are attributed to subtle variations in the distorted four-coordinate environments about the copper nuclei. The spans of the copper chemical shift (CS) tensors, δ11-δ33, for the mono- and bisphosphine complexes are also similar, ranging from 1000 to 1150 ppm, but that for a complex with a strained bidentate phosphine ligand is only 650 ppm. The effects of residual dipolar and indirect spin-spin coupling arising from the (63/65)Cu- (31)P spin pairs, observed in the solid-state (31)P NMR spectra of these complexes, yield information about the orientations of the copper electric field gradient (EFG) tensors relative to the Cu-P bond. Variable-temperature (31)P NMR measurements for [Cu(bptzH)(dppe)]ClO4 (bptzH = 5-tert-butyl-3-(2'-pyridyl)-1,2,4-triazole; dppe = 1,2-bis(diphenylphosphino)ethane), undertaken to investigate the cause of the broad unresolved spectra observed at room temperature, demonstrate that the broadening arises from partial self-decoupling of the (63/65)Cu nuclei, a consequence of rapid quadrupolar relaxation. Ab initio calculations of copper EFG and CS tensors were performed to probe relationships between NMR parameters and molecular structure. The analysis demonstrated that CQ((63/65)Cu) is negative for all complexes studied here and that the largest components of the EFG tensors are generally coincident with δ11.

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Section: Introductionmentioning

confidence: 99%

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Tan

Bernard

et al. 2015

J. Phys. Chem. A

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“…Rh(CO) 2 Cp*, the only compound herein with an h 5coordinated cyclopentadienyl ring, has a d iso = −1150 ppm, the lowest in this set, which is indicative of an extremely shielded 103 Rh nucleus as is typical for d iso values of metal nuclides in metallocenes. [132][133][134][135] The relationships between the 103 Rh chemical shi tensor parameters and structure and bonding in this set of Rh complexes is further explored with DFT calculations (see Sections 3.2 and 3.3).…”

Section: Resultsmentioning

confidence: 99%

Structure and bonding in rhodium coordination compounds: a ¹⁰³Rh solid-state NMR and relativistic DFT study

Holmes,

Schönzart,

Philips

et al. 2024

Chem. Sci.

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Sensitivity and Resolution Enhancement of Half-integer Quadrupolar Nuclei in Solid-state NMR

Nakashima¹,

Wasylishen²

2011

Encyclopedia of Magnetic Resonance

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Solid-state NMR Spectroscopy in Organometallic Chemistry

Cited by 6 publications

References 250 publications

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Structure and bonding in rhodium coordination compounds: a ¹⁰³Rh solid-state NMR and relativistic DFT study

Sensitivity and Resolution Enhancement of Half-integer Quadrupolar Nuclei in Solid-state NMR

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Solid-state NMR Spectroscopy in Organometallic Chemistry

Cited by 6 publications

References 250 publications

Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Structure and bonding in rhodium coordination compounds: a 103Rh solid-state NMR and relativistic DFT study

Sensitivity and Resolution Enhancement of Half-integer Quadrupolar Nuclei in Solid-state NMR

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Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Structure and bonding in rhodium coordination compounds: a ¹⁰³Rh solid-state NMR and relativistic DFT study