Synthesis, spectroscopy and electrochemistry of rhenium(V) imido complexes of pyridine and a comparative study with oxo and nitrido analogues; crystal structure of [Rev(NMe)(py)3(OEt)Cl]ClO4(py = pyridine)

Yam, Vivian Wing‐Wah; Tam, Kwok-Kwong; Cheung, Kung‐Kai

doi:10.1039/dt9950002779

Cited by 7 publications

(5 citation statements)

References 18 publications

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“…A single progression of broad peaks is observed in all spectra with an average spacing between 1075 and 1100 cm -1 and with an experimental uncertainty in choosing the peak maxima of ±100 cm -1 . These values are within the range of rhenium−nitrogen triple bonds reported in the literature. ,− …”

Section: Discussionsupporting

confidence: 85%

“…(c) Assignment of Rhenium − Nitrogen (ReN) Stretching Mode in Raman and IR Spectra. The range of reported nitridorhenium bond stretching frequencies is 1000−1100 cm -1 . ,− However, the assignment of the ReN stretching frequency is complicated by the interference of modes from the other ligands. Only the ReN bond is common to the four complexes under investigation; the other ligands are common to two complexes each, allowing for the identification of their modes.…”

Section: Discussionmentioning

confidence: 99%

“…Since the transition places an electron in the ReN π*, the bond length change is expected to be positive. Therefore, the ReN bond length is 0.084 Å longer in the excited state than in the electronic ground state, or approximately 1.68 Å. Crystallographic determinations of ReN bond lengths report that the difference between the bond lengths when the bond order is 3 and 2.5 is approximately 0.082 Å (bonds of bond order 3 have an average length of 1.633 Å, ,,, and bonds between a bond order of 2 and 3 have an average length of 1.715 Å ,, ). The good agreement shows that the bond order changes in the excited states are consistent with a reduction from 3 to 2.5.…”

Section: Discussionmentioning

confidence: 99%

“…The series of compounds investigated all produce structured emission spectra upon excitation at low temperature. Nitridorhenium(V) compounds are known to luminesce, ,− and some have been observed to produce vibronic structure. ,, The structure has been assigned to the ReN vibration, ,, but the excited state has never been analyzed. Detailed assignments of the modes involved in the emitting state will allow for an estimate of the ReN bond length change in the excited state.…”

Section: Introductionmentioning

confidence: 99%

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Excited-State Distortions Determined from Structured Luminescence of Nitridorhenium(V) Complexes

et al. 2002

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The nitridorhenium(V) complexes ReNCl(2)(PCy3)(2) (1), ReNBr(2)(PCy3)(2) (2), ReNCl(2)(PPh3)(2) (3), and ReNBr(2)(PPh3)(2) (4) produce structured emission spectra upon excitation at low temperature. The origin, E(00), occurs at 15 775, 16 375, 15 875, and 16 300 cm(-1), respectively. The vibronic peaks are regularly spaced with an average energy separation corresponding to the Re triple bond N stretching frequency. The nitridorhenium stretching frequency ranges from 1095 to 1101 cm(-1), as determined by Raman and IR spectroscopy. The excited-state distortions are calculated by fitting the emission spectra. The excited state arises primarily from a d(xy) (ReN nonbonding) to d(yz) (ReN pi antibonding) transition. The rhenium-nitrogen bond length in the excited state is 0.08 A longer than in the ground electronic state, which is consistent with the difference in bond lengths of ReN bonds of bond order 3 and bond order 2.5 as determined from molecular structures.

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Section: Discussionsupporting

confidence: 85%

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Excited-State Distortions Determined from Structured Luminescence of Nitridorhenium(V) Complexes

et al. 2002

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“…This indicates partial double bond character and transfer of π-electron density from the Re⋮N bond to the trans-situated Re−O bond. This has previously been observed for a number of oxorhenium complexes with trans-bonded alkoxo ligands 40 and a few examples of imido complexes . For nitrido species, however, it is without precedent.…”

Section: Resultsmentioning

confidence: 56%

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

et al. 2005

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Air-stable rhenium(V) nitrido complexes are formed when [ReOCl3(PPh3)2], [NBu4][ReOCl4], or [NBu4][ReNCl4] are treated with an excess of silylated phosphoraneiminates of the composition Me3SiNPPh3 or Ph2P(NSiMe3)CH2PPh2 in CH2Cl2. Complexes of the compositions [ReNCl(Ph2PCH2PPh2NH)2]Cl (1), [ReN(OSiMe3)(Ph2PCH2PPh2NH)2]Cl (2) or [ReNCl2(PPh3)2] (3) were isolated and structurally characterized. The latter compound was also produced during a reaction of the rhenium(III) precursor [ReCl3(PPh3)2(CH3CN)] and Me3SiNPPh3. Nitrogen transfer from the phosphorus to the rhenium atoms and the formation of nitrido ligands were observed in all examples. All products of reactions with an excess of the potentially chelating phosphoraneiminate Me3SiNP(Ph2)CH2PPh2 contain neutral Ph2PCH2PPh2NH ligands. The required protons are supplied by a metal-induced decomposition of the solvent dichloromethane. The Re-N(imine) bond lengths (2.055-2.110 A) indicate single bonds, whereas the N-P bond with lengths between 1.596 A and 1.611 A reflect considerable double bond character. An oxorhenium(V) phosphoraneiminato complex, the dimeric compound [ReOCl2(mu-N-Ph2PCH2PPh2N)]2 (4), is formed during the reaction of [NBu4][ReOCl4] with an equivalent amount of Ph2P(NSiMe3)CH2PPh in dry acetonitrile. The blue neutral complex with two bridging phosphoraneiminato units is stable as a solid and in dry solvents. It decomposes in solution, when traces of water are present. The rhenium-nitrogen distances of 2.028(3) and 2.082(3) A are in the typical range of bridging phosphoraneiminates and an almost symmetric bonding mode. Technetium complexes with phosphoraneimine ligands were isolated from reactions of [NBu4][TcOCl4] with Me3SiNPPh3, and [NBu4][TcNCl4] with Me3SiNP(Ph2)CH2PPh2. Nitrogen transfer and the formation of a five-coordinate nitrido species, [TcNCl2(HNPPh3)2] (5), was observed in the case of the oxo precursor, whereas reduction of the technetium(VI) starting material and the formation of the neutral technetium(V) complex [TcNCl2(Ph2PCH2PPh2NH)] (6) or [TcNCl(Ph2PCH2PPh2NH)2]Cl (7) was observed in the latter case. Both technetium complexes are air stable and X-ray structure determinations show bonding modes of the phosphoraneimines similar to those in the rhenium complexes.

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Synthesis and Reactivity of Structurally Analogous Phenylimido and Oxo Complexes of Rhenium(V) with N,N‐Dialkyl‐N′‐benzoylthioureas

Huy

Abram

2008

Zeitschrift anorg allge chemie

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[ReOCl3(PPh3)2] and [Re(NPh)Br3(PPh3)2] react at room temperature with equivalent amounts of N,N‐dialkyl‐N′‐benzoylthioureas (HR1R2btu) in CH2Cl2 under formation of the rhenium(V) complexes [ReOCl2(R1R1btu)(PPh3)] and [Re(NPh)Br2(R1R2btu)(PPh3)], respectively. The products are structurally analogous with the oxygen atoms of the benzoylthioureas binding in trans positions to the oxo or phenylimido ligands. Prolonged reaction times result in the reduction of the oxo compound by the released PPh3 and the formation of rhenium(III) complexes of the composition [ReCl2(PPh3)2(R1R2btu)], while such a second reaction path is excluded for the phenylimido compound. Phenylimido species with more than one N,N‐dialkyl‐N′‐benzoylthioureato ligand could not be isolated, even when a large excess of HR1R2btu was used during the reaction.

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Synthesis, spectroscopy and electrochemistry of rhenium(V) imido complexes of pyridine and a comparative study with oxo and nitrido analogues; crystal structure of [Rev(NMe)(py)3(OEt)Cl]ClO4(py = pyridine)

Cited by 7 publications

References 18 publications

Excited-State Distortions Determined from Structured Luminescence of Nitridorhenium(V) Complexes

Excited-State Distortions Determined from Structured Luminescence of Nitridorhenium(V) Complexes

Rhenium(V) and Technetium(V) Complexes with Phosphoraneimine and Phosphoraneiminato Ligands

Synthesis and Reactivity of Structurally Analogous Phenylimido and Oxo Complexes of Rhenium(V) with N,N‐Dialkyl‐N′‐benzoylthioureas

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