Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN) (tBuNC)4] units

Wolfgang Imhof; Anke Sterzik; Sven Krieck; Markus Schwierz; Thomas Hoffeld; Eike T. Spielberg; Winfried Plass; Nathan Patmore

doi:10.1039/b923536a

Intramolecular electron transfer in cyanide bridged adducts comprising Ru^II/Ru^III tetracarboxylate and [Mn^I(CO)(CN) (^tBuNC)₄] units

Wolfgang Imhof, Anke Sterzik, Sven Krieck, Markus Schwierz, Thomas Hoffeld, Eike T. Spielberg, Winfried Plass, Nathan Patmore

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

8 Citations (Scopus)

Abstract

Reaction of mixed valence ruthenium tetracarboxylates [Ru₂ ^II,III(R¹COO)₂(R²COO)₂Cl] (R¹ = Me, R² = 2,4,6-ⁱPr-Ph or R¹ = R² = ^tBu) with two equivalents of the octahedral manganese complex [Mn^I(CO)(CN)(^tBuNC)₄] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru₂^II,III(R¹COO) ₂(R²COO)₂][Mn^I(CO)(CN)( ^tBuNC)₄]₂}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru₂ core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {Mn^I-Ru₂^II,III-Mn^I}⁺ adduct into {Mn^II-Ru₂^II,III-Mn ^I}²⁺ and {Mn^I-Ru₂ ^II,II-Mn^I} species cannot be completely ruled out.

Original language	English
Pages (from-to)	6249-6254
Number of pages	6
Journal	Dalton Transactions
Volume	39
Issue number	27
DOIs	https://doi.org/10.1039/b923536a
Publication status	Published - 21 Jul 2010
Externally published	Yes

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@article{ed8d02b01fc24f7796841e2b007f1c1a,

title = "Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN) (tBuNC)4] units",

abstract = "Reaction of mixed valence ruthenium tetracarboxylates [Ru2 II,III(R1COO)2(R2COO)2Cl] (R1 = Me, R2 = 2,4,6-iPr-Ph or R1 = R2 = tBu) with two equivalents of the octahedral manganese complex [MnI(CO)(CN)(tBuNC)4] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru2II,III(R1COO) 2(R2COO)2][MnI(CO)(CN)( tBuNC)4]2}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru2 core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {MnI-Ru2II,III-MnI}+ adduct into {MnII-Ru2II,III-Mn I}2+ and {MnI-Ru2 II,II-MnI} species cannot be completely ruled out.",

author = "Wolfgang Imhof and Anke Sterzik and Sven Krieck and Markus Schwierz and Thomas Hoffeld and Spielberg, {Eike T.} and Winfried Plass and Nathan Patmore",

year = "2010",

month = jul,

day = "21",

doi = "10.1039/b923536a",

language = "English",

volume = "39",

pages = "6249--6254",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "27",

}

TY - JOUR

T1 - Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN) (tBuNC)4] units

AU - Imhof, Wolfgang

AU - Sterzik, Anke

AU - Krieck, Sven

AU - Schwierz, Markus

AU - Hoffeld, Thomas

AU - Spielberg, Eike T.

AU - Plass, Winfried

AU - Patmore, Nathan

PY - 2010/7/21

Y1 - 2010/7/21

N2 - Reaction of mixed valence ruthenium tetracarboxylates [Ru2 II,III(R1COO)2(R2COO)2Cl] (R1 = Me, R2 = 2,4,6-iPr-Ph or R1 = R2 = tBu) with two equivalents of the octahedral manganese complex [MnI(CO)(CN)(tBuNC)4] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru2II,III(R1COO) 2(R2COO)2][MnI(CO)(CN)( tBuNC)4]2}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru2 core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {MnI-Ru2II,III-MnI}+ adduct into {MnII-Ru2II,III-Mn I}2+ and {MnI-Ru2 II,II-MnI} species cannot be completely ruled out.

AB - Reaction of mixed valence ruthenium tetracarboxylates [Ru2 II,III(R1COO)2(R2COO)2Cl] (R1 = Me, R2 = 2,4,6-iPr-Ph or R1 = R2 = tBu) with two equivalents of the octahedral manganese complex [MnI(CO)(CN)(tBuNC)4] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru2II,III(R1COO) 2(R2COO)2][MnI(CO)(CN)( tBuNC)4]2}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru2 core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {MnI-Ru2II,III-MnI}+ adduct into {MnII-Ru2II,III-Mn I}2+ and {MnI-Ru2 II,II-MnI} species cannot be completely ruled out.

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U2 - 10.1039/b923536a

DO - 10.1039/b923536a

M3 - Article

AN - SCOPUS:77954282285

VL - 39

SP - 6249

EP - 6254

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 27

ER -

Intramolecular electron transfer in cyanide bridged adducts comprising Ru^II/Ru^III tetracarboxylate and [Mn^I(CO)(CN) (^tBuNC)₄] units

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