X-ray diffraction investigation of nonbonding interactions and coordination in organometallic compounds

Bokii, N. G.; Udel'nov, A. I.; Struchkov, Yu. T.; Kravtsov, D. N.; Pachevskaya, V. M.

doi:10.1007/bf00745472

Cited by 8 publications

(6 citation statements)

References 11 publications

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“…1). While this bonding mode of a monomeric nitrosoaryl was already observed with other metal ions, [16][17][18][19][20][21] the present non-disordered structures are the first examples with Cu and the first with an O-bonded unsubstituted nitrosobenzene. 22,23 The [1] + complexes in the two crystal structures differ mainly by the arrangement of the phenyl ring with respect to the Cu-O-N linkage.…”

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confidence: 66%

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The two spin states of an end-on copper(ii)-superoxide mimic

et al. 2011

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confidence: 66%

“…CCDC-815281, C 19 H 35 CuF 3 N 5 O 4 S, M = 550.12, orthorhombic, a = 10.5615 (11), b = 13.7600 (14), c = 17.3141(18) A ˚, U = 2516.2(5) A ˚3, T = 111 K space group P2 1 2 1 2 1 (no. 19), Z = 4, 25370 reflections measured, 4632 unique (R int = 0.0484) which were used in all calculations. The final wR(F 2 ) was 0.0751 (all data).…”

Section: Notes and Referencesmentioning

confidence: 99%

The two spin states of an end-on copper(ii)-superoxide mimic

et al. 2011

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“…The O -binding of C -nitroso compounds is much less common (Table ). Complexes of formulation C in Figure are now known for monomeric compounds containing Sn 168 or Zn 169 and for a polymeric complex of Pb . The O -binding mode has also been observed in porphyrin complexes of Fe III 161 and Mn III ; however, both these complexes display unusually short N−O bond lengths.…”

Section: Spectroscopy and Structurementioning

confidence: 91%

Interactions of Organic Nitroso Compounds with Metals

et al. 2002

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“…(ii) Most mononuclear κO complexes with non-d 10 transition metals are structurally disordered, ,,− and conclusive statements about the extent of back-donation and ArNO reduction cannot be made. By contrast, the nondisordered crystal structures of [(Me 6 tren)Cu(κO-PhNO)]X (X = TfO – , SbF 6 – ; Scheme b) show significant NO bond elongation.…”

Section: Introductionmentioning

confidence: 99%

Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

et al. 2020

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A series of copper/nitrosoarene complexes were created that mimic several steps in biomimetic O 2 activation by copper(I). The reaction of the copper(I) complex of N,N,N′,N′tetramethypropylenediamine with a series of para-substituted nitrosobenzene derivatives leads to adducts in which the nitrosoarene (ArNO) is reduced by zero, one, or two electrons, akin to the isovalent species dioxygen, superoxide, and peroxide, respectively. The geometric and electronic structures of these adducts were characterized by means of X-ray diffraction, vibrational analysis, ultraviolet−visible spectroscopy, NMR, electrochemistry, and density functional theory (DFT) calculations. The bonding mode of the NO moiety depends on the oxidation state of the ArNO moiety: κN for ArNO, mononuclear η 2-NO and dinuclear μ-η 2 :η 1 for ArNO •− , and dinuclear μ-η 2 :η 2 for ArNO 2−. 15 N isotopic labeling confirms the reduction state by measuring the NO stretching frequency (1392 cm −1 for κN-ArNO, 1226 cm −1 for η 2-ArNO •− , 1133 cm −1 for dinuclear μ-η 2 :η 1-ArNO •− , and 875 cm −1 for dinuclear μ-η 2 :η 2 for ArNO 2−). The 15 N NMR signal disappears for the ArNO •− species, establishing a unique diagnostic for the radical state. Electrochemical studies indicate reduction waves that are consistent with one-electron reduction of the adducts and are compared with studies performed on Cu-O 2 analogues. DFT calculations were undertaken to confirm our experimental findings, notably to establish the nature of the charge-transfer transitions responsible for the intense green color of the complexes. In fine, this family of complexes is unique in that it walks through three redox states of the ArNO moiety while keeping the metal and its supporting ligand the same. This work provides snapshots of the reactivity of the toxic nitrosoarene molecules with the biologically relevant Cu(I) ion. 47 usually too oxidative to be stable above −60°C.

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X-ray diffraction investigation of nonbonding interactions and coordination in organometallic compounds

Cited by 8 publications

References 11 publications

The two spin states of an end-on copper(ii)-superoxide mimic

The two spin states of an end-on copper(ii)-superoxide mimic

Interactions of Organic Nitroso Compounds with Metals

Tuning Inner-Sphere Electron Transfer in a Series of Copper/Nitrosoarene Adducts

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