Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph ...

Michael E. Wright, Thomas M. Mezza, Gregory O. Nelson, Neal R Armstrong, Victor W. Day, Michael R. Thompson

Research output: Contribution to journalArticle

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Abstract

Full title: Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph2P(CH 2)nPPh2] (n = 2, 3). Molecular structures of Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)nPPh2] where n = 1 and 3. Photolysis of Me2Si[η5-C5H4Fe(CO) 2]2 (1) with a series of bis(phosphines) (L = Ph2P(CH2)nPPh2, where n = 1, 2, and 3) leads to the formation of substituted dinuclear and tetranuclear compounds of the form Me2Si[η5-C5H4Fe(CO)] 2[L] and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[L], respectively. The ratio of these two types of compounds is dependent upon the ligand size (number of methylene units), stoichiometry, and the overall concentration employed. With the small ligands and dilute conditions, formation of the dinuclear product is favored. Under more concentrated reaction conditions and when an excess of 1 is used, the tetranuclear type of product becomes dominant. The electrochemistry of the dinuclear compounds indicate that both the silyl and the bis(phosphine) bridges are capable of stabilizing a two-electron oxidation product. This is demonstrated in the case of L = dppm where we observe, by fast-scan cyclic voltammetry, two, one-electron reversible oxidation steps. The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppm] (3a) is determined by X-ray diffraction. It crystallizes in the space group Pnma (No. 62) with a = 13.754 (4) Å, b = 17.707 (4) Å, c = 13.771 (3) Å and α, β, and γ = 90.00° with Z = 4. The structure was refined to R1 = 0.041 and R2 = 0.045 for 2226 independent reflections having I > 3σ(I). The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppp] (3c) is also determined by X-ray diffraction. It crystallizes in the space group P1 (No. 2) with a = 11.638 (11) Å, b = 11.833 (11) Å, c = 16.289 (14) Å, α = 111.22 (6)°, β = 72.67 (7)°, and γ = 107.02 (7)° with Z = 2. The structure is refined to R1 = 0.067 and R2 = 0.076 for 4115 independent reflections having I > 3σ(I). The overall geometry of 3a compared to 3c implies that some distortion occurs from the steric requirements of the larger dppp ligand. This includes a significant lengthening of the Fe-Fe bond in complex 3c by 0.024 (3) Å relative to 3a.

Original languageEnglish (US)
Pages (from-to)1711-1718
Number of pages8
JournalOrganometallics
Volume2
Issue number12
StatePublished - 1983

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Electrochemistry
Carbon Monoxide
electrochemistry
phosphines
ligands
synthesis
products
oxidation
diffraction
methylene
phosphine
photolysis
stoichiometry
electrons
x rays
molecular structure
Ligands
methylidyne
requirements
Phosphines

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph ... / Wright, Michael E.; Mezza, Thomas M.; Nelson, Gregory O.; Armstrong, Neal R; Day, Victor W.; Thompson, Michael R.

In: Organometallics, Vol. 2, No. 12, 1983, p. 1711-1718.

Research output: Contribution to journalArticle

Wright, Michael E. ; Mezza, Thomas M. ; Nelson, Gregory O. ; Armstrong, Neal R ; Day, Victor W. ; Thompson, Michael R. / Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph ... In: Organometallics. 1983 ; Vol. 2, No. 12. pp. 1711-1718.
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title = "Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph ...",
abstract = "Full title: Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph2P(CH 2)nPPh2] (n = 2, 3). Molecular structures of Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)nPPh2] where n = 1 and 3. Photolysis of Me2Si[η5-C5H4Fe(CO) 2]2 (1) with a series of bis(phosphines) (L = Ph2P(CH2)nPPh2, where n = 1, 2, and 3) leads to the formation of substituted dinuclear and tetranuclear compounds of the form Me2Si[η5-C5H4Fe(CO)] 2[L] and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[L], respectively. The ratio of these two types of compounds is dependent upon the ligand size (number of methylene units), stoichiometry, and the overall concentration employed. With the small ligands and dilute conditions, formation of the dinuclear product is favored. Under more concentrated reaction conditions and when an excess of 1 is used, the tetranuclear type of product becomes dominant. The electrochemistry of the dinuclear compounds indicate that both the silyl and the bis(phosphine) bridges are capable of stabilizing a two-electron oxidation product. This is demonstrated in the case of L = dppm where we observe, by fast-scan cyclic voltammetry, two, one-electron reversible oxidation steps. The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppm] (3a) is determined by X-ray diffraction. It crystallizes in the space group Pnma (No. 62) with a = 13.754 (4) {\AA}, b = 17.707 (4) {\AA}, c = 13.771 (3) {\AA} and α, β, and γ = 90.00° with Z = 4. The structure was refined to R1 = 0.041 and R2 = 0.045 for 2226 independent reflections having I > 3σ(I). The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppp] (3c) is also determined by X-ray diffraction. It crystallizes in the space group P1 (No. 2) with a = 11.638 (11) {\AA}, b = 11.833 (11) {\AA}, c = 16.289 (14) {\AA}, α = 111.22 (6)°, β = 72.67 (7)°, and γ = 107.02 (7)° with Z = 2. The structure is refined to R1 = 0.067 and R2 = 0.076 for 4115 independent reflections having I > 3σ(I). The overall geometry of 3a compared to 3c implies that some distortion occurs from the steric requirements of the larger dppp ligand. This includes a significant lengthening of the Fe-Fe bond in complex 3c by 0.024 (3) {\AA} relative to 3a.",
author = "Wright, {Michael E.} and Mezza, {Thomas M.} and Nelson, {Gregory O.} and Armstrong, {Neal R} and Day, {Victor W.} and Thompson, {Michael R.}",
year = "1983",
language = "English (US)",
volume = "2",
pages = "1711--1718",
journal = "Organometallics",
issn = "0276-7333",
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TY - JOUR

T1 - Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph ...

AU - Wright, Michael E.

AU - Mezza, Thomas M.

AU - Nelson, Gregory O.

AU - Armstrong, Neal R

AU - Day, Victor W.

AU - Thompson, Michael R.

PY - 1983

Y1 - 1983

N2 - Full title: Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph2P(CH 2)nPPh2] (n = 2, 3). Molecular structures of Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)nPPh2] where n = 1 and 3. Photolysis of Me2Si[η5-C5H4Fe(CO) 2]2 (1) with a series of bis(phosphines) (L = Ph2P(CH2)nPPh2, where n = 1, 2, and 3) leads to the formation of substituted dinuclear and tetranuclear compounds of the form Me2Si[η5-C5H4Fe(CO)] 2[L] and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[L], respectively. The ratio of these two types of compounds is dependent upon the ligand size (number of methylene units), stoichiometry, and the overall concentration employed. With the small ligands and dilute conditions, formation of the dinuclear product is favored. Under more concentrated reaction conditions and when an excess of 1 is used, the tetranuclear type of product becomes dominant. The electrochemistry of the dinuclear compounds indicate that both the silyl and the bis(phosphine) bridges are capable of stabilizing a two-electron oxidation product. This is demonstrated in the case of L = dppm where we observe, by fast-scan cyclic voltammetry, two, one-electron reversible oxidation steps. The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppm] (3a) is determined by X-ray diffraction. It crystallizes in the space group Pnma (No. 62) with a = 13.754 (4) Å, b = 17.707 (4) Å, c = 13.771 (3) Å and α, β, and γ = 90.00° with Z = 4. The structure was refined to R1 = 0.041 and R2 = 0.045 for 2226 independent reflections having I > 3σ(I). The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppp] (3c) is also determined by X-ray diffraction. It crystallizes in the space group P1 (No. 2) with a = 11.638 (11) Å, b = 11.833 (11) Å, c = 16.289 (14) Å, α = 111.22 (6)°, β = 72.67 (7)°, and γ = 107.02 (7)° with Z = 2. The structure is refined to R1 = 0.067 and R2 = 0.076 for 4115 independent reflections having I > 3σ(I). The overall geometry of 3a compared to 3c implies that some distortion occurs from the steric requirements of the larger dppp ligand. This includes a significant lengthening of the Fe-Fe bond in complex 3c by 0.024 (3) Å relative to 3a.

AB - Full title: Synthesis, characterization, and electrochemistry of the bis-bridged complexes Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)n PPh2] (n = 1-3) and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[Ph2P(CH 2)nPPh2] (n = 2, 3). Molecular structures of Me2Si[η5-C5H4Fe(CO)] 2[Ph2P(CH2)nPPh2] where n = 1 and 3. Photolysis of Me2Si[η5-C5H4Fe(CO) 2]2 (1) with a series of bis(phosphines) (L = Ph2P(CH2)nPPh2, where n = 1, 2, and 3) leads to the formation of substituted dinuclear and tetranuclear compounds of the form Me2Si[η5-C5H4Fe(CO)] 2[L] and [Me2Si[(η5-C5H4) 2Fe2(CO)3]]2[L], respectively. The ratio of these two types of compounds is dependent upon the ligand size (number of methylene units), stoichiometry, and the overall concentration employed. With the small ligands and dilute conditions, formation of the dinuclear product is favored. Under more concentrated reaction conditions and when an excess of 1 is used, the tetranuclear type of product becomes dominant. The electrochemistry of the dinuclear compounds indicate that both the silyl and the bis(phosphine) bridges are capable of stabilizing a two-electron oxidation product. This is demonstrated in the case of L = dppm where we observe, by fast-scan cyclic voltammetry, two, one-electron reversible oxidation steps. The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppm] (3a) is determined by X-ray diffraction. It crystallizes in the space group Pnma (No. 62) with a = 13.754 (4) Å, b = 17.707 (4) Å, c = 13.771 (3) Å and α, β, and γ = 90.00° with Z = 4. The structure was refined to R1 = 0.041 and R2 = 0.045 for 2226 independent reflections having I > 3σ(I). The structure of Me2Si[η5-C5H4Fe(CO)] 2[dppp] (3c) is also determined by X-ray diffraction. It crystallizes in the space group P1 (No. 2) with a = 11.638 (11) Å, b = 11.833 (11) Å, c = 16.289 (14) Å, α = 111.22 (6)°, β = 72.67 (7)°, and γ = 107.02 (7)° with Z = 2. The structure is refined to R1 = 0.067 and R2 = 0.076 for 4115 independent reflections having I > 3σ(I). The overall geometry of 3a compared to 3c implies that some distortion occurs from the steric requirements of the larger dppp ligand. This includes a significant lengthening of the Fe-Fe bond in complex 3c by 0.024 (3) Å relative to 3a.

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