New octahedral rhenium(I) tricarbonyl amido complexes

E Hevia, J Perez, V Riera, D Miguel

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

Several new Re(I) octahedral amido complexes fac-[Re(NRR')(CO)(3)(N-N)1 (R = aryl; R' = H, aryl; N-N = 2,2-bipyridine, bipy; 1,10-phenanthroline, phen) have been synthesized either by reaction of [Re(OTf)(CO)(3)(N-N)] precursors with potassium amides or by deprotonation of [Re(NH2Ar)(CO)(3)(N-N)OTf compounds, in turn obtained by reaction of [Re(OTf)(CO)(3)(N-N)] compounds with amines. The structure of the amido complexes [Re(NHPh)(CO)3(bipy)] (5) and [Re(NPh2)(CO)(3)(bipy)] (6) have been determined by single-crystal X-ray diffraction. The results, coupled with the solution NMR behavior of the complexes, indicate that the delocalization of the nitrogen lone pair of the amido group involves mainly the N-aryl bonds. Amido complexes [Re(NEp-Tol)(CO)(3)(N-N)] (4a,b) (p-Tol = 4-methylphenyl) react with 4-ethylphenol, with ethanothiol, and with diphenylphosphine to give the complexes [Re(OC6H4-4-C2H5)(CO)(3)(bipy)] (8), [Re(SCH2CH3)(CO)(3)(bipy)] (9), and [Re(PPh2)(CO)(3)(N-N)] (10a,b). The structure of the diphenylphosphido complex [Re(Ph-2)(CO)(3)(phen)] (10b), determined by X-ray diffraction, was compared with the structure of the homologous diphenylamido complex 6. The different geometries (pyramidal phosphorus and planar amido nitrogen) correlate with the higher nucleophilicity of the phosphido complex.

LanguageEnglish
Pages1966-1974
Number of pages9
JournalOrganometallics
Volume21
Issue number9
DOIs
Publication statusPublished - 29 Apr 2002

Fingerprint

Rhenium
rhenium
Carbon Monoxide
nitrogen
diffraction
amides
phosphorus
potassium
amines
x rays
nuclear magnetic resonance
single crystals
geometry
Nitrogen
X ray diffraction
Deprotonation
Amides
Phosphorus
Amines
Potassium

Keywords

  • transition-metal chemistry
  • carbonyl-diimine complexes
  • ligands
  • photoinduced reduction
  • reactivity

Cite this

Hevia, E ; Perez, J ; Riera, V ; Miguel, D . / New octahedral rhenium(I) tricarbonyl amido complexes. In: Organometallics. 2002 ; Vol. 21, No. 9. pp. 1966-1974.
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Hevia, E, Perez, J, Riera, V & Miguel, D 2002, 'New octahedral rhenium(I) tricarbonyl amido complexes' Organometallics, vol. 21, no. 9, pp. 1966-1974. https://doi.org/10.1021/om0110383

New octahedral rhenium(I) tricarbonyl amido complexes. / Hevia, E ; Perez, J ; Riera, V ; Miguel, D .

In: Organometallics, Vol. 21, No. 9, 29.04.2002, p. 1966-1974.

Research output: Contribution to journalArticle

TY - JOUR

T1 - New octahedral rhenium(I) tricarbonyl amido complexes

AU - Hevia, E

AU - Perez, J

AU - Riera, V

AU - Miguel, D

PY - 2002/4/29

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N2 - Several new Re(I) octahedral amido complexes fac-[Re(NRR')(CO)(3)(N-N)1 (R = aryl; R' = H, aryl; N-N = 2,2-bipyridine, bipy; 1,10-phenanthroline, phen) have been synthesized either by reaction of [Re(OTf)(CO)(3)(N-N)] precursors with potassium amides or by deprotonation of [Re(NH2Ar)(CO)(3)(N-N)OTf compounds, in turn obtained by reaction of [Re(OTf)(CO)(3)(N-N)] compounds with amines. The structure of the amido complexes [Re(NHPh)(CO)3(bipy)] (5) and [Re(NPh2)(CO)(3)(bipy)] (6) have been determined by single-crystal X-ray diffraction. The results, coupled with the solution NMR behavior of the complexes, indicate that the delocalization of the nitrogen lone pair of the amido group involves mainly the N-aryl bonds. Amido complexes [Re(NEp-Tol)(CO)(3)(N-N)] (4a,b) (p-Tol = 4-methylphenyl) react with 4-ethylphenol, with ethanothiol, and with diphenylphosphine to give the complexes [Re(OC6H4-4-C2H5)(CO)(3)(bipy)] (8), [Re(SCH2CH3)(CO)(3)(bipy)] (9), and [Re(PPh2)(CO)(3)(N-N)] (10a,b). The structure of the diphenylphosphido complex [Re(Ph-2)(CO)(3)(phen)] (10b), determined by X-ray diffraction, was compared with the structure of the homologous diphenylamido complex 6. The different geometries (pyramidal phosphorus and planar amido nitrogen) correlate with the higher nucleophilicity of the phosphido complex.

AB - Several new Re(I) octahedral amido complexes fac-[Re(NRR')(CO)(3)(N-N)1 (R = aryl; R' = H, aryl; N-N = 2,2-bipyridine, bipy; 1,10-phenanthroline, phen) have been synthesized either by reaction of [Re(OTf)(CO)(3)(N-N)] precursors with potassium amides or by deprotonation of [Re(NH2Ar)(CO)(3)(N-N)OTf compounds, in turn obtained by reaction of [Re(OTf)(CO)(3)(N-N)] compounds with amines. The structure of the amido complexes [Re(NHPh)(CO)3(bipy)] (5) and [Re(NPh2)(CO)(3)(bipy)] (6) have been determined by single-crystal X-ray diffraction. The results, coupled with the solution NMR behavior of the complexes, indicate that the delocalization of the nitrogen lone pair of the amido group involves mainly the N-aryl bonds. Amido complexes [Re(NEp-Tol)(CO)(3)(N-N)] (4a,b) (p-Tol = 4-methylphenyl) react with 4-ethylphenol, with ethanothiol, and with diphenylphosphine to give the complexes [Re(OC6H4-4-C2H5)(CO)(3)(bipy)] (8), [Re(SCH2CH3)(CO)(3)(bipy)] (9), and [Re(PPh2)(CO)(3)(N-N)] (10a,b). The structure of the diphenylphosphido complex [Re(Ph-2)(CO)(3)(phen)] (10b), determined by X-ray diffraction, was compared with the structure of the homologous diphenylamido complex 6. The different geometries (pyramidal phosphorus and planar amido nitrogen) correlate with the higher nucleophilicity of the phosphido complex.

KW - transition-metal chemistry

KW - carbonyl-diimine complexes

KW - ligands

KW - photoinduced reduction

KW - reactivity

U2 - 10.1021/om0110383

DO - 10.1021/om0110383

M3 - Article

VL - 21

SP - 1966

EP - 1974

JO - Organometallics

T2 - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 9

ER -