Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH3)Fe(CO)(P(CH3)3)2]2. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCHCOOCH3)][B(C6H5)4]

J. J. Bonnet; R. Mathieu; James A. Ibers

doi:10.1021/ic50210a052

Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]

J. J. Bonnet, R. Mathieu, James A. Ibers

Chemistry

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

14 Scopus citations

Abstract

The synthesis and structure from IR and NMR data of the complex (μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH₃COOCCCOOCH₃) are described, and its reactivity toward H⁺ is studied. Protonation gives a chelated (C, O) 1, 2-bis(carbomethoxy)ethylene complex in which the added proton is cis to the carbon-bonded iron atom. The structure of the product has been established by a crystal structure determination of [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CEI₃COOCCHCOOCH₃)][B(C₆H5)₄]. In this complex each iron atom is octahedrally coordinated to two bridging sulfur atoms of the methylthiolato groups, two phosphine ligands trans to the sulfur atoms, one carbonyl group, and a vinylic carbon atom for one iron atom and an oxygen atom of the α-carbonyl ester group for the other. The compound crystallizes with 4 formula units in the monoclinic space group C⁵_2h-P2₁/c in a cell of dimensions a = 10.716 (4) Å, b = 30.227 (11) Å, c = 16, 346 (5) Å, and β = 102.75 (1)°. On the basis of 5856 unique reflections, the structure was refined by full-matrix least-squares techniques to conventional indices (on F) of R = 0.050 and R_w = 0.057. The Fe-Fe separation of 3.452 (1) Å and the dihedral angle around the sulfur atoms of 157.8° lead to the widest spacing thus far found for this type of dinuclear, sulfur-bridged iron complex.

Original language	English (US)
Pages (from-to)	2448-2453
Number of pages	6
Journal	Inorganic chemistry
Volume	19
Issue number	8
DOIs	https://doi.org/10.1021/ic50210a052
State	Published - 1980

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Bonnet, J. J., Mathieu, R., & Ibers, J. A. (1980). Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]. Inorganic chemistry, 19(8), 2448-2453. https://doi.org/10.1021/ic50210a052

Bonnet, J. J. ; Mathieu, R. ; Ibers, James A. / Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]. In: Inorganic chemistry. 1980 ; Vol. 19, No. 8. pp. 2448-2453.

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title = "Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH3)Fe(CO)(P(CH3)3)2]2. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCHCOOCH3)][B(C6H5)4]",

abstract = "The synthesis and structure from IR and NMR data of the complex (μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCCOOCH3) are described, and its reactivity toward H+ is studied. Protonation gives a chelated (C, O) 1, 2-bis(carbomethoxy)ethylene complex in which the added proton is cis to the carbon-bonded iron atom. The structure of the product has been established by a crystal structure determination of [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CEI3COOCCHCOOCH3)][B(C6H5)4]. In this complex each iron atom is octahedrally coordinated to two bridging sulfur atoms of the methylthiolato groups, two phosphine ligands trans to the sulfur atoms, one carbonyl group, and a vinylic carbon atom for one iron atom and an oxygen atom of the α-carbonyl ester group for the other. The compound crystallizes with 4 formula units in the monoclinic space group C52h-P21/c in a cell of dimensions a = 10.716 (4) {\AA}, b = 30.227 (11) {\AA}, c = 16, 346 (5) {\AA}, and β = 102.75 (1)°. On the basis of 5856 unique reflections, the structure was refined by full-matrix least-squares techniques to conventional indices (on F) of R = 0.050 and Rw = 0.057. The Fe-Fe separation of 3.452 (1) {\AA} and the dihedral angle around the sulfur atoms of 157.8° lead to the widest spacing thus far found for this type of dinuclear, sulfur-bridged iron complex.",

author = "Bonnet, {J. J.} and R. Mathieu and Ibers, {James A.}",

year = "1980",

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Bonnet, JJ, Mathieu, R & Ibers, JA 1980, 'Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]', Inorganic chemistry, vol. 19, no. 8, pp. 2448-2453. https://doi.org/10.1021/ic50210a052

Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]. / Bonnet, J. J.; Mathieu, R.; Ibers, James A.
In: Inorganic chemistry, Vol. 19, No. 8, 1980, p. 2448-2453.

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

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T1 - Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH3)Fe(CO)(P(CH3)3)2]2. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCHCOOCH3)][B(C6H5)4]

AU - Bonnet, J. J.

AU - Mathieu, R.

AU - Ibers, James A.

PY - 1980

Y1 - 1980

N2 - The synthesis and structure from IR and NMR data of the complex (μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCCOOCH3) are described, and its reactivity toward H+ is studied. Protonation gives a chelated (C, O) 1, 2-bis(carbomethoxy)ethylene complex in which the added proton is cis to the carbon-bonded iron atom. The structure of the product has been established by a crystal structure determination of [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CEI3COOCCHCOOCH3)][B(C6H5)4]. In this complex each iron atom is octahedrally coordinated to two bridging sulfur atoms of the methylthiolato groups, two phosphine ligands trans to the sulfur atoms, one carbonyl group, and a vinylic carbon atom for one iron atom and an oxygen atom of the α-carbonyl ester group for the other. The compound crystallizes with 4 formula units in the monoclinic space group C52h-P21/c in a cell of dimensions a = 10.716 (4) Å, b = 30.227 (11) Å, c = 16, 346 (5) Å, and β = 102.75 (1)°. On the basis of 5856 unique reflections, the structure was refined by full-matrix least-squares techniques to conventional indices (on F) of R = 0.050 and Rw = 0.057. The Fe-Fe separation of 3.452 (1) Å and the dihedral angle around the sulfur atoms of 157.8° lead to the widest spacing thus far found for this type of dinuclear, sulfur-bridged iron complex.

AB - The synthesis and structure from IR and NMR data of the complex (μ-SCH3)Fe(CO)(P(CH3)3)2)2(CH3COOCCCOOCH3) are described, and its reactivity toward H+ is studied. Protonation gives a chelated (C, O) 1, 2-bis(carbomethoxy)ethylene complex in which the added proton is cis to the carbon-bonded iron atom. The structure of the product has been established by a crystal structure determination of [((μ-SCH3)Fe(CO)(P(CH3)3)2)2(CEI3COOCCHCOOCH3)][B(C6H5)4]. In this complex each iron atom is octahedrally coordinated to two bridging sulfur atoms of the methylthiolato groups, two phosphine ligands trans to the sulfur atoms, one carbonyl group, and a vinylic carbon atom for one iron atom and an oxygen atom of the α-carbonyl ester group for the other. The compound crystallizes with 4 formula units in the monoclinic space group C52h-P21/c in a cell of dimensions a = 10.716 (4) Å, b = 30.227 (11) Å, c = 16, 346 (5) Å, and β = 102.75 (1)°. On the basis of 5856 unique reflections, the structure was refined by full-matrix least-squares techniques to conventional indices (on F) of R = 0.050 and Rw = 0.057. The Fe-Fe separation of 3.452 (1) Å and the dihedral angle around the sulfur atoms of 157.8° lead to the widest spacing thus far found for this type of dinuclear, sulfur-bridged iron complex.

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Bonnet JJ, Mathieu R, Ibers JA. Electrophilic Addition of a Proton to 1, 2-Bis(Carbomethoxy)Acetylene Inserted into the Iron-Iron Bond of [(μ-SCH₃)Fe(CO)(P(CH₃)₃)₂]₂. X-Ray Structure at -162°C of the Reaction Product, a Chelated 1, 2-Bis(Carbomethoxy)Ethylene Complex, [((μ-SCH₃)Fe(CO)(P(CH₃)₃)₂)₂(CH³COOCCHCOOCH₃)][B(C₆H₅)₄]. Inorganic chemistry. 1980;19(8):2448-2453. doi: 10.1021/ic50210a052