Copper(I) complexes—III

Lewin, Anita H.; Cohen, Ilan; Michl, Rudolf J.

doi:10.1016/0022-1902(74)80707-4

Cited by 19 publications

(2 citation statements)

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“…Tetrakis(4-picoline)copper(I) hexafluorophosphate, [Cu(pic) 4 ]PF 6 ( V ), was prepared by dissolving [Cu(acn) 4 ][PF 6 ] in redistilled 4-picoline under argon and then adding diethyl ether to form a precipitate, which was separated by filtration. Proportions of all reactants used were the same as for the synthesis of II .…”

Section: Methodsmentioning

confidence: 99%

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

1996

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Described are the photophysical properties of the mononuclear copper(I) complexes CuL(4)(+) (L = pyridine (py), 4-methylpyridine, 4-phenylpyridine, or acetonitrile), Cu(lut)(3)(+) (lut = 2,6-lutidine), and Cu(lut)(2)(+). Each of these compounds as their solid PF(6)(-) salts display a relatively long-lived (>1 &mgr;s), visible range emission at both ambient temperature and at 77 K but not in fluid solutions. Also reported are the results for ab initio calculations at the restricted Hartree-Fock self-consistent field level to probe the natures of lower energy excited states of the hypothetical species CuL(n)()(+) (L = NH(3), CH(3)CN, or py; n = 1-4). These results point to an assignment of the lowest energy, luminactive excited states as being largely metal centered, d --> s in character for each of the above complexes with the possible exception of the CuL(4)(+) species where L is py or a substituted analogue. In the case of Cu(py)(4)(+) the ab initiocalculations indicate a metal-to-ligand charge transfer to be the lowest energy Franck-Condon state, although the similarities of emission band shapes, energies, and lifetimes among the various complexes suggest a common d --> s assignment.

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Section: Methodsmentioning

confidence: 99%

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

1996

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“…The preparation of these salts has been described previously. 28 Nitrogen Evolution Measurements. The procedure described by Siggia for nitrogen measurement was followed.…”

Section: Methodsmentioning

confidence: 99%

Reduction products in copper(I)-promoted diazonium ion reactions. Hydrogen abstraction from amines coordinated to copper(I), from water, and from transient radicals

Lewin¹,

Peterson²,

Michl³

1974

J. Org. Chem.

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Reduction products are observed in amine-copper(I) perchlorate promoted decomposition of aryldiazonium salts when the amine ligands are capable of hydrogen atom donation. The effective reducing agents evidently are the complexed rather than the free ligands, i.e., the tris(amine)copperd) cation in the case of tetraand tricoordinated salts and the bis(amine)copper(I) cation in the dicoordinated systems, in the presence of excess ligand a new product is obtained, which is probably an ammonium salt formed from the amine and the incipient aryl cation. In the absence of hydrogen-donating ligands it has been shown that the small but consistent amount of benzophenone formed in the copper®-promoted decomposition of 2-diazobenzophenone tetrafluoroborate arises from (a) the precursor to 9-fluorenone and (b) the solvent, water. Hydrogen atom abstraction from both these sources is rate determining and subject to a kinetic isotope effect. Since water is a notoriously poor hydrogen atom donor, transfer of a hydrogen atom from the equated coordination sphere of copper® via a bridged intermediate is postulated.

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Alkylquinolines and Arylquinolines

Claret

Osborne

1982

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Copper(I) complexes—III

Cited by 19 publications

References 19 publications

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

Photophysical andab InitioStudies of Mononuclear Copper(I) Complexes

Reduction products in copper(I)-promoted diazonium ion reactions. Hydrogen abstraction from amines coordinated to copper(I), from water, and from transient radicals

Alkylquinolines and Arylquinolines

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