Cu NUCLEAR QUADRUPOLE RESONANCES OF SEVERAL COMPLEXES OF COPPER(I) HALIDES WITH TRIPHENYLPHOSPHINE

Okuda, Takuo; Hiura, Morio; Yamada, Koji; Negita, Hisao

doi:10.1246/cl.1977.367

Cited by 15 publications

(9 citation statements)

References 8 publications

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“…As we [1] and others [2,3] have shown, the 63,65 Cu NQR resonance frequencies of such complexes are highly dependent on the coordination number. Thus the complexes (L 2 X)" of cuprous halides with phosphine [2,3] or pyridine [1] ligands may be tricoordinated and monomeric, showing a 63 Cu NQR frequency around 35 MHz, or be tetracoordinated halogen-bridged dimers showing a 63 Cu NQR frequency around 15 MHz.…”

Section: Introductionsupporting

confidence: 53%

The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

Habiyakare

Lücken

1990

Zeitschrift Für Naturforschung A

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The NQR frequencies of the 63 65 Cu nuclei in di-coordinated complex cations of Cu 1 , having the general formula CuL 2 X, where L is a substituted pyridine and X is a hard anion such as C10 4 , are reported and discussed in the light of the known crystal structures. A departure from a strictly linear geometry of the L 2 Cu cation has but little effect on the resonance frequency, but the donor-acceptor bond between the nitrate anion and the copper atom in bis(2,6-lutidine)cuprous nitrate, which was postulated on crystallographic grounds, is confirmed by the NQR results, which also indicate a similar interaction in bis(2,6-lutidine)cuprous trifluoroacetate. A number of the complexes discussed here have not been reported previously.

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Section: Introductionsupporting

confidence: 53%

The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

Habiyakare

Lücken

1990

Zeitschrift Für Naturforschung A

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“…Similar values have been previously reported in NQR studies. 34,111,112 For the three-coordinate environment, V 33 should be oriented perpendicular to the molecular trigonal plane. Although the X-Cu bond lengths are approximately the same for the respective compounds, ca.…”

Section: Resultsmentioning

confidence: 99%

“…Copper sites of low symmetry with large quadrupolar interactions have chiefly been characterized with nuclear quadrupolar resonance (NQR). NQR has been used to probe copper sites in inorganic salts, 6 copper halides, [33][34][35][36][37] high-temperature superconductors, [38][39][40][41] and magnetic materials. [42][43][44][45] While routine NQR experiments can provide extremely accurate measurements of the quadrupolar coupling constant (C Q ), the asymmetry parameter (η Q ) is only accessible through technically demanding, two-dimensional NQR experiments.…”

Section: Introductionmentioning

confidence: 99%

Solid-State⁶³Cu and⁶⁵Cu NMR Spectroscopy of Inorganic and Organometallic Copper(I) Complexes

et al. 2007

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Solid-state 63Cu and 65Cu NMR experiments have been conducted on a series of inorganic and organometallic copper(I) complexes possessing a variety of spherically asymmetric two-, three-, and four-coordinate Cu coordination environments. Variations in structure and symmetry, and corresponding changes in the electric field gradient (EFG) tensors, yield 63/65Cu quadrupolar coupling constants (CQ) ranging from 22.0 to 71.0 MHz for spherically asymmetric Cu sites. These large quadrupolar interactions result in spectra featuring quadrupolar-dominated central transition patterns with breadths ranging from 760 kHz to 6.7 MHz. Accordingly, Hahn-echo and/or QCPMG pulse sequences were applied in a frequency-stepped manner to rapidly acquire high S/N powder patterns. Significant copper chemical shielding anisotropies (CSAs) are also observed in some cases, ranging from 1000 to 1500 ppm. 31P CP/MAS NMR spectra for complexes featuring 63/65Cu-31P spin pairs exhibit residual dipolar coupling and are simulated to determine both the sign of CQ and the EFG tensor orientations relative to the Cu-P bond axes. X-ray crystallographic data and theoretical (Hartree-Fock and density functional theory) calculations of 63/65Cu EFG and CS tensors are utilized to examine the relationships between NMR interaction tensor parameters, the magnitudes and orientations of the principal components, and molecular structure and symmetry.

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“…This suggests that the copper quadrupole coupling constants are quite different for the two different co-ordination environments (P,CuBr, and P,CuBr) involved, despite the fact that the co-ordination number is four in both cases. In the 'step' form of [Cu(PPh,)Br], the nuclear quadrupole resonance frequency of the trigonally co-ordinated copper atom has been measured, 16 and is almost identical to that of the trigonal copper atom in [( Ph,P)CuBr,Cu(PPh,),] and one quartet for the unsolvated 'step' [Cu(PPh,)Br], has a Avij which is comparable in magnitude to the values for the trigonal sites in the other compounds in Table 4 and the other to the tetrahedral PCuBr, site.…”

Section: Discussionmentioning

confidence: 99%

Synthesis and characterization of the novel copper(I) anion [Cu(PPh3)Br2]?

Bowmaker¹,

Skelton²,

White³

et al. 1988

J. Chem. Soc., Dalton Trans.

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Solid-state 31 P n.m.r., far-i.r. spectroscopy and single-crystal X-ray diffraction techniques have been used to characterize a new type of ionic copper(I) compound: [ PPh,Me] [Cu (PPh,) Br,]. X-Ray analysis shows the PPh, ligand to be coordinated to the copper atom of the CuBr, unit in a trigonal planar arrangement, with CuP 2.21 0(3), Cu-Br 2.367(2), 2.386(2) A and Br-Cu-Br 11 4.9(1)" {monoclinic, space group Pn, a = 11.779(5), b = 9.914(5), c = 14.705(10) A, p = 94.92(5)", Z = 2, R = 0.037 for 1 570 'observed' [ I > 30(/)] reflections}. The far-i.r. spectrum shows a strong band at 195 cm-l assigned to the antisymmetric Cu-Br stretching mode of the CuBr, unit, and a weaker band at 150 cm-I assigned to the symmetric Cu-Br stretching mode. This assignment is supported by an approximate normal-coordinate analysis, and the resulting Cu-Br force constant is compared with values obtained in similar analyses of related bromocopper(I) complexes. The cross-polarization magic angle spinning 31 P n.m.r. spectrum shows a strong signal at 21 p.p.m. (relative to 85% H,PO,) due to the cation, and a weaker quartet centred at-1 4 p.p.m. due to the coordinated PPh, in the anion, with line spacings due to CuP coupling of 1.37,1.69, and 1.92 kHz.

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Cu NUCLEAR QUADRUPOLE RESONANCES OF SEVERAL COMPLEXES OF COPPER(I) HALIDES WITH TRIPHENYLPHOSPHINE

Abstract: The 63Cu nuclear quadrupole resonances have been observed in (CuX)nLm (X=Cl, Br, I; L=triphenylphosphine; n:m=1:1, 2:3, 1:2). Two characteristic frequency ranges were observed: the resonance frequencies of the three-coordinated Cu atoms are far above those of the four-coordinated.

Cited by 15 publications

References 8 publications

The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

Solid-State⁶³Cu and⁶⁵Cu NMR Spectroscopy of Inorganic and Organometallic Copper(I) Complexes

Synthesis and characterization of the novel copper(I) anion [Cu(PPh3)Br2]?

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Cu NUCLEAR QUADRUPOLE RESONANCES OF SEVERAL COMPLEXES OF COPPER(I) HALIDES WITH TRIPHENYLPHOSPHINE

Abstract: The 63Cu nuclear quadrupole resonances have been observed in (CuX)nLm (X=Cl, Br, I; L=triphenylphosphine; n:m=1:1, 2:3, 1:2). Two characteristic frequency ranges were observed: the resonance frequencies of the three-coordinated Cu atoms are far above those of the four-coordinated.

Cited by 15 publications

References 8 publications

The 63,65Cu NQR Spectra of Di-coordinated CuI Cations with 2-Substituted Pyridine Ligands

The 63,65Cu NQR Spectra of Di-coordinated CuI Cations with 2-Substituted Pyridine Ligands

Solid-State63Cu and65Cu NMR Spectroscopy of Inorganic and Organometallic Copper(I) Complexes

Synthesis and characterization of the novel copper(I) anion [Cu(PPh3)Br2]?

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The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

The ^63,65Cu NQR Spectra of Di-coordinated Cu^I Cations with 2-Substituted Pyridine Ligands

Solid-State⁶³Cu and⁶⁵Cu NMR Spectroscopy of Inorganic and Organometallic Copper(I) Complexes