Multielectron Transfer and Single-Crystal X-ray Structure of a Trinuclear Cyanide-Bridged Platinum–Iron Species

Meisheng Zhou; Brian W. Pfennig; Jana Steiger; Donna Van Engen; Andrew Bruce Bocarsly

doi:10.1021/ic00338a014

Multielectron Transfer and Single-Crystal X-ray Structure of a Trinuclear Cyanide-Bridged Platinum–Iron Species

Meisheng Zhou, Brian W. Pfennig, Jana Steiger, Donna Van Engen, Andrew Bruce Bocarsly

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59 Scopus citations

Abstract

[Pt(NH₃)₄]₂[(NC)5Fe^II–CN–Pt^Iv(NH3)₄–NC–Fe^II(CN)₅]•9H₂O was synthesized by the redox reaction of Pt(NH₃)₄(NO₃)₂ and K₃Fe(CN)₆ in aqueous solution. The red complex crystallized in space group P2₁/c (No. 14) and was analyzed by X-ray diffractometry. The monoclinic crystal consists of a trinuclear, cyanide-bridged Fe–Pt–Fe anion hydrogen-bonded via a terminal cyanide group on each iron atom to two separate tetraammineplatinum(II) counterions. Unit cell dimensions are a = 15.313 (2) Å, b = 8.5353 (14) Å, c = 16.206 (5) Å, β = 100.52 (2)°, and Z = 2; a center of inversion exists at the central Pt atom of the trinuclear anion. The R factors for this structure are R = 5.0% and R_w = 5.3%. On the basis of infrared spectroscopy, magnetic measurements, ESR spectroscopy, and the electrochemistry of the compound, localized oxidation states of Fe^II–Pt^IV–Fe^II are assigned to the complex. The electronic spectrum reveals an intervalent (IT) charge-transfer absorption at approximately 470 nm. Excitation into this band effects an electron transfer between the Fe¹¹ and Pt^Iv atoms and results in the formation of Pt(NH₃)₄²⁺ and ferricyanide in a 1 to 2 ratio. The initial quantum yield for the formation of ferricyanide at 488-nm irradiation is 0.02.

Original language	English (US)
Pages (from-to)	2456-2460
Number of pages	5
Journal	Inorganic Chemistry
Volume	29
Issue number	13
DOIs	https://doi.org/10.1021/ic00338a014
State	Published - Jun 1 1990

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic00338a014

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@article{8833af6ebd41481097a4bbb928c658eb,

title = "Multielectron Transfer and Single-Crystal X-ray Structure of a Trinuclear Cyanide-Bridged Platinum–Iron Species",

abstract = "[Pt(NH3)4]2[(NC)5FeII–CN–PtIv(NH3)4–NC–FeII(CN)5]•9H2O was synthesized by the redox reaction of Pt(NH3)4(NO3)2 and K3Fe(CN)6 in aqueous solution. The red complex crystallized in space group P21/c (No. 14) and was analyzed by X-ray diffractometry. The monoclinic crystal consists of a trinuclear, cyanide-bridged Fe–Pt–Fe anion hydrogen-bonded via a terminal cyanide group on each iron atom to two separate tetraammineplatinum(II) counterions. Unit cell dimensions are a = 15.313 (2) {\AA}, b = 8.5353 (14) {\AA}, c = 16.206 (5) {\AA}, β = 100.52 (2)°, and Z = 2; a center of inversion exists at the central Pt atom of the trinuclear anion. The R factors for this structure are R = 5.0% and Rw = 5.3%. On the basis of infrared spectroscopy, magnetic measurements, ESR spectroscopy, and the electrochemistry of the compound, localized oxidation states of FeII–PtIV–FeII are assigned to the complex. The electronic spectrum reveals an intervalent (IT) charge-transfer absorption at approximately 470 nm. Excitation into this band effects an electron transfer between the Fe11 and PtIv atoms and results in the formation of Pt(NH3)42+ and ferricyanide in a 1 to 2 ratio. The initial quantum yield for the formation of ferricyanide at 488-nm irradiation is 0.02.",

author = "Meisheng Zhou and Pfennig, {Brian W.} and Jana Steiger and {Van Engen}, Donna and Bocarsly, {Andrew Bruce}",

year = "1990",

month = jun,

day = "1",

doi = "10.1021/ic00338a014",

language = "English (US)",

volume = "29",

pages = "2456--2460",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

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TY - JOUR

T1 - Multielectron Transfer and Single-Crystal X-ray Structure of a Trinuclear Cyanide-Bridged Platinum–Iron Species

AU - Zhou, Meisheng

AU - Pfennig, Brian W.

AU - Steiger, Jana

AU - Van Engen, Donna

AU - Bocarsly, Andrew Bruce

PY - 1990/6/1

Y1 - 1990/6/1

N2 - [Pt(NH3)4]2[(NC)5FeII–CN–PtIv(NH3)4–NC–FeII(CN)5]•9H2O was synthesized by the redox reaction of Pt(NH3)4(NO3)2 and K3Fe(CN)6 in aqueous solution. The red complex crystallized in space group P21/c (No. 14) and was analyzed by X-ray diffractometry. The monoclinic crystal consists of a trinuclear, cyanide-bridged Fe–Pt–Fe anion hydrogen-bonded via a terminal cyanide group on each iron atom to two separate tetraammineplatinum(II) counterions. Unit cell dimensions are a = 15.313 (2) Å, b = 8.5353 (14) Å, c = 16.206 (5) Å, β = 100.52 (2)°, and Z = 2; a center of inversion exists at the central Pt atom of the trinuclear anion. The R factors for this structure are R = 5.0% and Rw = 5.3%. On the basis of infrared spectroscopy, magnetic measurements, ESR spectroscopy, and the electrochemistry of the compound, localized oxidation states of FeII–PtIV–FeII are assigned to the complex. The electronic spectrum reveals an intervalent (IT) charge-transfer absorption at approximately 470 nm. Excitation into this band effects an electron transfer between the Fe11 and PtIv atoms and results in the formation of Pt(NH3)42+ and ferricyanide in a 1 to 2 ratio. The initial quantum yield for the formation of ferricyanide at 488-nm irradiation is 0.02.

AB - [Pt(NH3)4]2[(NC)5FeII–CN–PtIv(NH3)4–NC–FeII(CN)5]•9H2O was synthesized by the redox reaction of Pt(NH3)4(NO3)2 and K3Fe(CN)6 in aqueous solution. The red complex crystallized in space group P21/c (No. 14) and was analyzed by X-ray diffractometry. The monoclinic crystal consists of a trinuclear, cyanide-bridged Fe–Pt–Fe anion hydrogen-bonded via a terminal cyanide group on each iron atom to two separate tetraammineplatinum(II) counterions. Unit cell dimensions are a = 15.313 (2) Å, b = 8.5353 (14) Å, c = 16.206 (5) Å, β = 100.52 (2)°, and Z = 2; a center of inversion exists at the central Pt atom of the trinuclear anion. The R factors for this structure are R = 5.0% and Rw = 5.3%. On the basis of infrared spectroscopy, magnetic measurements, ESR spectroscopy, and the electrochemistry of the compound, localized oxidation states of FeII–PtIV–FeII are assigned to the complex. The electronic spectrum reveals an intervalent (IT) charge-transfer absorption at approximately 470 nm. Excitation into this band effects an electron transfer between the Fe11 and PtIv atoms and results in the formation of Pt(NH3)42+ and ferricyanide in a 1 to 2 ratio. The initial quantum yield for the formation of ferricyanide at 488-nm irradiation is 0.02.

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U2 - 10.1021/ic00338a014

DO - 10.1021/ic00338a014

M3 - Article

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SN - 0020-1669

VL - 29

SP - 2456

EP - 2460

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 13

ER -

Multielectron Transfer and Single-Crystal X-ray Structure of a Trinuclear Cyanide-Bridged Platinum–Iron Species

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