Preparation and Characterization of the Triflate Complex [Cp*(dppe)FeOSO2CF3]: A Convenient Access to Labile Five- and Six-Coordinate Iron(I) and Iron(II) Complexes

被引：9

作者：

Hamon, Paul ^{[1
]}

Toupet, Loic ^{[2
]}

Roisnel, Thierry ^{[1
]}

Hamon, Jean-Rene ^{[1
]}

Lapinte, Claude ^{[1
]}

机构：

[1] Univ Rennes, CNRS, ISCR UMR 6226, F-35000 Rennes, France

[2] Univ Rennes, CNRS, IPR UMR 6251, F-35000 Rennes, France

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2020年 / 2020卷 / 01期

关键词：

Iron; Triflate adducts; N; O ligands; Structure elucidation; Coordination modes; RAY CRYSTAL-STRUCTURES; MOLECULAR-STRUCTURE; MAGNETIC-PROPERTIES; DINITROGEN COMPLEX; METAL-COMPLEXES; BOUND LIGANDS; LOW-SPIN; HYDRIDE; MOSSBAUER; RUTHENIUM;

D O I：

10.1002/ejic.201901086

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Treatment of the iron hydride [Cp*(dppe)FeH] (1) with methyl triflate (CH3OSO2CF3) yielded the iron triflate adduct [Cp*(dppe)FeOSO2CF3] (4, 85 %). In the solid state, the triflate is coordinated at the iron center as shown by XRD (d(Fe-O) = 2.118(4) angstrom) and IR spectroscopy (nu(SO) = 1305 cm(-1)). In solution, 4 is in equilibrium with the 16-electron species [Cp*(dppe)Fe]OSO2CF3 (5(OSO2CF3)), 4/5(OSO2CF3) = 2:1). The CV of 4 displays two waves (E-1 = -0.74 V, E-2 = 0.24 V vs. SCE) assigned to the [Cp*(dppe)Fe(I)]/[Cp*(dppe)Fe(II)](+) and [Cp*(dppe)Fe(II)](+)/[Cp*(dppe)Fe(III)](2+) redox couples. Reduction of 4 with Cp2Co provided the complex [Cp*(dppe)Fe(I)] (6, 95 %) and oxidation of 6 with [Cp2Fe]PF6 gave [Cp*(dppe)Fe]PF6 (5(PF6), 98 %). XRD established the pseudo-trigonal bipyramidal geometry for the five-coordinated cation 5(+). The reactivity of 5(PF6) and 6 toward small molecules (CH2Cl2, H2O, CO, H-2, N-2) is reported.

引用

页码：84 / 93

页数：10

共 14 条

[1] Formation and characterization of five- and six-coordinate iron(III) corrolazine complexes
Kurahashi, Satoshi
Ikeue, Takahisa
Sugimori, Tamotsu
Takahashi, Masashi
Mikuriya, Masahiro
Handa, Makoto
Ikezaki, Akira
Nakamura, Mikio
[J]. JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, 2012, 16 (5-6) : 518 - 529
[2] (Nitrosyl)iron(II) porphyrinates: structural characterization and temperature-dependent Mossbauer studies of a series of five- and six-coordinate complexes.
Wyllie, GRA
Schulz, CE
Scheidt, WR
[J]. JOURNAL OF INORGANIC BIOCHEMISTRY, 2001, 86 (01) : 484 - 484
[3] Spin density distribution in five- and six-coordinate iron(II)-porphyrin NO complexes evidenced by magnetic circular dichroism spectroscopy
Praneeth, VKK
Neese, F
Lehnert, N
[J]. INORGANIC CHEMISTRY, 2005, 44 (08) : 2570 - 2572
[4] Semi-empirical AM1 and PM3 calculations of five- and six-coordinate oxo iron (IV) porphyrin complexes
Katagi, T
[J]. JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2005, 728 (1-3): : 49 - 56
[5] Synthesis and structural characterization of five- and six-coordinate cobalt(II) complexes of tripodal ligand, tris-(2-benzimidazolylmethyl)amine
Lah, MS
Moon, M
[J]. BULLETIN OF THE KOREAN CHEMICAL SOCIETY, 1997, 18 (04) : 406 - 409
[6] Syntheses and X-ray crystal structures of five- and six-coordinated iron(I) and iron(II) complexes with the same (eta(5)-C(5)Me(5))Fe(dppe) framework
Hamon, P
Toupet, L
Hamon, JR
Lapinte, C
[J]. ORGANOMETALLICS, 1996, 15 (01) : 10 - 12
[7] New five- and six-coordinate nitrosylosmium(0) and nitrosylosmium(II) complexes prepared from the stable 16-electron species [OsCl(NO)(PR(3))(2)]
Werner, H
Flugel, R
Windmuller, B
[J]. CHEMISCHE BERICHTE-RECUEIL, 1997, 130 (04): : 493 - 505
[8] Synthesis, characterization, antifungal properties and X-ray crystal structures of five- and six-coordinate copper(II) complexes of the 6-methyl-2-formylpyridine4N-dimethylthiosemicarbazone
Ali, MA
Mirza, AH
Hossain, AMS
Nazimuddin, M
[J]. POLYHEDRON, 2001, 20 (9-10) : 1045 - 1052
[9] Syntheses and X-ray crystal structures of five- and six-coordinate copper(II) complexes of N,N,N',N'-tetraalkylpyridine-2,6-dicarboxamides containing-OClO3 and-OSO2CF3 counter ions
Kapoor, Pratibha
Pannu, Ajay Pal Singh
Sharma, Mukesh
Hundal, Maninder Singh
Kapoor, Ramesh
[J]. JOURNAL OF COORDINATION CHEMISTRY, 2010, 63 (20) : 3635 - 3647
[10] Five- and six-coordinate ruthenium(II) complexes containing 2-Ph2PC6H4CH=NtBu and 2-Ph2PC6H4CH2NHtBu as chelate ligands:: Synthesis, characterization, and catalytic activity in transfer hydrogenation of ketones
Crochet, P
Gimeno, J
García-Granda, S
Borge, J
[J]. ORGANOMETALLICS, 2001, 20 (21) : 4369 - 4377

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