Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)3(μ3-E)2, E = S, Se

Richard D. Adams; Shaobin Miao; Mark D. Smith; Horatio Farach; Charles Edwin Webster; Josiah Manson; Michael B. Hall

doi:10.1021/ic0354419

Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp₂Ni ₂Mn(CO)₃(μ₃-E)₂, E = S, Se

Richard D. Adams, Shaobin Miao, Mark D. Smith, Horatio Farach, Charles Edwin Webster, Josiah Manson, Michael B. Hall

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

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Abstract

The reaction of Mn₂(CO)₇(μ-S₂) with [CpNi(CO)]₂ yielded the paramagnetic new compound Cp ₂Ni₂Mn(CO)₃(μ₃-S)₂ (1) and a new hexanuclear metal product Cp₂Ni₂Mn ₄(CO)₁₄(μ₆-S₂)(μ ₃-S)₂ (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni₂Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp₂Ni₂Mn(CO)₃(μ₃-Se)₂ (3) was obtained from the reaction of a mixture of Mn₂(CO) ₁₀ and [CpNi(CO)]₂ with elemental selenium and Me ₃NO·₂H₂O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp₂Ni₂Mn ₂(CO)₆(μ₄-S₂)(μ ₄-S₅), 4, which can also be made from the reaction of Mn₂(CO)₇(μ-S₂) with [CpNi(CO)]₂ and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh₃. The reaction of Mn₂(CO)₁₀ with [CpNi(CO)]₂ in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)₃(μ-SCH₂CH₂S) (5), which was also obtained from the reaction of Mn₄(CO)₁₅(μ ₃-S₂)(μ₄-S₂) with [CpNi-(CO)]₂ in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) ₃[μ-S(CH₂CH₂S)₂], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn₂(CO) ₁₀ with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

Original language	English (US)
Pages (from-to)	2515-2525
Number of pages	11
Journal	Inorganic Chemistry
Volume	43
Issue number	8
DOIs	https://doi.org/10.1021/ic0354419
State	Published - Apr 19 2004
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{cd384e5b87b8459f801662dc67e7e8a1,

title = "Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)3(μ3-E)2, E = S, Se",

abstract = "The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.",

author = "Adams, {Richard D.} and Shaobin Miao and Smith, {Mark D.} and Horatio Farach and Webster, {Charles Edwin} and Josiah Manson and Hall, {Michael B.}",

year = "2004",

month = apr,

day = "19",

doi = "10.1021/ic0354419",

language = "English (US)",

volume = "43",

pages = "2515--2525",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

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TY - JOUR

T1 - Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp2Ni 2Mn(CO)3(μ3-E)2, E = S, Se

AU - Adams, Richard D.

AU - Miao, Shaobin

AU - Smith, Mark D.

AU - Farach, Horatio

AU - Webster, Charles Edwin

AU - Manson, Josiah

AU - Hall, Michael B.

PY - 2004/4/19

Y1 - 2004/4/19

N2 - The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

AB - The reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 yielded the paramagnetic new compound Cp 2Ni2Mn(CO)3(μ3-S)2 (1) and a new hexanuclear metal product Cp2Ni2Mn 4(CO)14(μ6-S2)(μ 3-S)2 (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni2Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp2Ni2Mn(CO)3(μ3-Se)2 (3) was obtained from the reaction of a mixture of Mn2(CO) 10 and [CpNi(CO)]2 with elemental selenium and Me 3NO·2H2O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp2Ni2Mn 2(CO)6(μ4-S2)(μ 4-S5), 4, which can also be made from the reaction of Mn2(CO)7(μ-S2) with [CpNi(CO)]2 and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh3. The reaction of Mn2(CO)10 with [CpNi(CO)]2 in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)3(μ-SCH2CH2S) (5), which was also obtained from the reaction of Mn4(CO)15(μ 3-S2)(μ4-S2) with [CpNi-(CO)]2 in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO) 3[μ-S(CH2CH2S)2], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn2(CO) 10 with CpNi(CO)12 and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses.

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EP - 2525

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Nickel-Manganese Sulfido Carbonyl Cluster Complexes. Synthesis, Structure, and Properties of the Unusual Paramagnetic Complexes Cp₂Ni ₂Mn(CO)₃(μ₃-E)₂, E = S, Se

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