Synthesis, structure, and reactivity of paramagnetic iron(II) and iron(III) amidodiphosphine complexes

Michael D. Fryzuk; Daniel B. Leznoff; Erin S.F. Ma; Steven J. Rettig; Victor G. Young

doi:10.1021/om970665i

Synthesis, structure, and reactivity of paramagnetic iron(II) and iron(III) amidodiphosphine complexes

Michael D. Fryzuk, Daniel B. Leznoff, Erin S.F. Ma, Steven J. Rettig, Victor G. Young

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

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Abstract

The preparation and characterization of a series of divalent and trivalent iron complexes that incorporate the amidodiphosphine ligand N(SiMe₂CH₂PPh₂)₂ are reported. Mononuclear, tetrahedral complexes of the type FeX[N(SiMe₂CH₂PPH₂)₂], where X = Cl, Br, have been prepared; magnetic susceptibility studies indicate that these are high-spin d⁶ systems. The preparation of Fe(II) alkyls of the formula FeR[N(SiMe₂CH₂PPh₂)₂] was examined; small alkyl substituents such as R = Me or CH₂Ph were found to be thermally unstable and, thus, not isolable; however, for R = CH₂SiMe₃ and CH(SiMe₃)₂, room-temperature stable, yellow, paramagnetic solids could be obtained. The reaction of FeCl[N(SiMe₂CH₂PPh₂)₂] with NaCp·-DME generates the thermally stable, diamagnetic complex Fe(η⁵-C₅H₅)[N(SiMe₂CH ₂PPh₂)₂]. The corresponding Fe(III) derivative FeX₂[N(SiMe₂CH₂PPh₂)₂] could be prepared in high yield by direct reaction of the LiN(SiMe₂CH₂PPH₂)₂ ligand precursor with either FeCl₃ or FeBr₃. Variable-temperature magnetic susceptibility studies indicate that FeBr₂[N(SiMe₂-CH₂PPh₂)₂] is an example of a spin-admixed system (S = 3/2 and 5/2 spin states).

Original language	English (US)
Pages (from-to)	2313-2323
Number of pages	11
Journal	Organometallics
Volume	17
Issue number	11
DOIs	https://doi.org/10.1021/om970665i
State	Published - May 25 1998

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title = "Synthesis, structure, and reactivity of paramagnetic iron(II) and iron(III) amidodiphosphine complexes",

abstract = "The preparation and characterization of a series of divalent and trivalent iron complexes that incorporate the amidodiphosphine ligand N(SiMe2CH2PPh2)2 are reported. Mononuclear, tetrahedral complexes of the type FeX[N(SiMe2CH2PPH2)2], where X = Cl, Br, have been prepared; magnetic susceptibility studies indicate that these are high-spin d6 systems. The preparation of Fe(II) alkyls of the formula FeR[N(SiMe2CH2PPh2)2] was examined; small alkyl substituents such as R = Me or CH2Ph were found to be thermally unstable and, thus, not isolable; however, for R = CH2SiMe3 and CH(SiMe3)2, room-temperature stable, yellow, paramagnetic solids could be obtained. The reaction of FeCl[N(SiMe2CH2PPh2)2] with NaCp·-DME generates the thermally stable, diamagnetic complex Fe(η5-C5H5)[N(SiMe2CH 2PPh2)2]. The corresponding Fe(III) derivative FeX2[N(SiMe2CH2PPh2)2] could be prepared in high yield by direct reaction of the LiN(SiMe2CH2PPH2)2 ligand precursor with either FeCl3 or FeBr3. Variable-temperature magnetic susceptibility studies indicate that FeBr2[N(SiMe2-CH2PPh2)2] is an example of a spin-admixed system (S = 3/2 and 5/2 spin states).",

author = "Fryzuk, {Michael D.} and Leznoff, {Daniel B.} and Ma, {Erin S.F.} and Rettig, {Steven J.} and Young, {Victor G.}",

year = "1998",

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T1 - Synthesis, structure, and reactivity of paramagnetic iron(II) and iron(III) amidodiphosphine complexes

AU - Fryzuk, Michael D.

AU - Leznoff, Daniel B.

AU - Ma, Erin S.F.

AU - Rettig, Steven J.

AU - Young, Victor G.

PY - 1998/5/25

Y1 - 1998/5/25

N2 - The preparation and characterization of a series of divalent and trivalent iron complexes that incorporate the amidodiphosphine ligand N(SiMe2CH2PPh2)2 are reported. Mononuclear, tetrahedral complexes of the type FeX[N(SiMe2CH2PPH2)2], where X = Cl, Br, have been prepared; magnetic susceptibility studies indicate that these are high-spin d6 systems. The preparation of Fe(II) alkyls of the formula FeR[N(SiMe2CH2PPh2)2] was examined; small alkyl substituents such as R = Me or CH2Ph were found to be thermally unstable and, thus, not isolable; however, for R = CH2SiMe3 and CH(SiMe3)2, room-temperature stable, yellow, paramagnetic solids could be obtained. The reaction of FeCl[N(SiMe2CH2PPh2)2] with NaCp·-DME generates the thermally stable, diamagnetic complex Fe(η5-C5H5)[N(SiMe2CH 2PPh2)2]. The corresponding Fe(III) derivative FeX2[N(SiMe2CH2PPh2)2] could be prepared in high yield by direct reaction of the LiN(SiMe2CH2PPH2)2 ligand precursor with either FeCl3 or FeBr3. Variable-temperature magnetic susceptibility studies indicate that FeBr2[N(SiMe2-CH2PPh2)2] is an example of a spin-admixed system (S = 3/2 and 5/2 spin states).

AB - The preparation and characterization of a series of divalent and trivalent iron complexes that incorporate the amidodiphosphine ligand N(SiMe2CH2PPh2)2 are reported. Mononuclear, tetrahedral complexes of the type FeX[N(SiMe2CH2PPH2)2], where X = Cl, Br, have been prepared; magnetic susceptibility studies indicate that these are high-spin d6 systems. The preparation of Fe(II) alkyls of the formula FeR[N(SiMe2CH2PPh2)2] was examined; small alkyl substituents such as R = Me or CH2Ph were found to be thermally unstable and, thus, not isolable; however, for R = CH2SiMe3 and CH(SiMe3)2, room-temperature stable, yellow, paramagnetic solids could be obtained. The reaction of FeCl[N(SiMe2CH2PPh2)2] with NaCp·-DME generates the thermally stable, diamagnetic complex Fe(η5-C5H5)[N(SiMe2CH 2PPh2)2]. The corresponding Fe(III) derivative FeX2[N(SiMe2CH2PPh2)2] could be prepared in high yield by direct reaction of the LiN(SiMe2CH2PPH2)2 ligand precursor with either FeCl3 or FeBr3. Variable-temperature magnetic susceptibility studies indicate that FeBr2[N(SiMe2-CH2PPh2)2] is an example of a spin-admixed system (S = 3/2 and 5/2 spin states).

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Synthesis, structure, and reactivity of paramagnetic iron(II) and iron(III) amidodiphosphine complexes

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