A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S-C6H4)]- stabilized by S,S π-donation from chelating [S,S-C6H4]2-

Chien Ming Lee, Ging Yi Lin, Chung Hung Hsieh, Ching Han Hu, Gene Hsiang Lee, Shie Ming Peng, Wen Feng Liaw

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Abstract

The five-coordinate, sixteen-electron manganese(I) complex [N(PPh3)2][Mn(CO)3(S,S-C6H 4)] 1 was prepared from reaction of [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] and 1,2-benzenedithiol via the hexacoordinate intermediate fac-[Mn(CO)3(S-C6H4SH)(NH2,S-C 6H4)]-. Alternatively, oxidative addition of 1,2-benzenedithiol to [Mn(CO)5]-, followed by a Lewis acid-base reaction, with evolution of H2 gas (identified by gas chromatography), led to formation of the coordinatively-unsaturated complex 1. In contrast, reaction of bis(2-pyridyl) disulfide and [N(PPh3)2][Mn(CO)5] afforded hexacoordinate fac-[N(PPh3)2][Mn(CO)3(S-C5H 4-N)(S-C5H4N)] 2, with one anionic [S-C5H4N]- ligand bound to MnI in a monodentate (S-bonded) manner and the other [S-C5H4-N]- ligand bound in a bidentate manner (S,N-bonded). Complexes 1 and 2 have been characterized in solution by infrared spectroscopy and in the solid state by X-ray crystallography. The strong π-donating ability of the bidentate [S,S-C6H4]2- ligand stabilizes the unsaturated complex 1 which has short MnI-S bond lengths of 2.230(1) Å (average) as a result. The existence of one π and two σ bonds between the [Mn(CO)3]+ and [S,S-C6H4]2- fragments, based on qualitative frontier molecular orbital analysis, also indicates that the lone-pair electrons are delocalized around the sulfur-manganese-sulfur system stabilizing the five-coordinate complex 1. The IR carbonyl stretching frequencies and the MnI-S bond distances of complexes 1 and [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] suggest that the relative π-donating ability of the bidentate ligands is [NH,S-C6H4]2- > [S,S-C6H4]2-. The Mulliken atomic charges derived from Hartree-Fock calculations roughly quantify the charge distribution in the complex [Mn(CO)3(NH,S-C6H4)]- (δ(N) = -1.14; δ(S) = -0.43; δ(Mn) = 1.14), and supports the premise that the reactions of [Mn(CO)3(NH,S-C6H4)]- with electrophiles (1,2-benzenedithiol, thiophene-2-thiol, 1,2-ethanedithiol) occur at the more electron-rich amide site, yielding charge-controlled, collision complexes.

Original languageEnglish
Pages (from-to)2393-2398
Number of pages6
JournalJournal of the Chemical Society - Dalton Transactions
Issue number14
DOIs
Publication statusPublished - 1999 Jul 21

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Carbon Monoxide
Manganese
Chelation
Electrons
Ligands
Sulfur
Thiophenes
Lewis Acids
X ray crystallography
Charge distribution
Bond length
Molecular orbitals
Sulfhydryl Compounds
Amides
Disulfides
Gas chromatography
Stretching
Infrared spectroscopy
Gases

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Lee, Chien Ming ; Lin, Ging Yi ; Hsieh, Chung Hung ; Hu, Ching Han ; Lee, Gene Hsiang ; Peng, Shie Ming ; Liaw, Wen Feng. / A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S-C6H4)]- stabilized by S,S π-donation from chelating [S,S-C6H4]2-. In: Journal of the Chemical Society - Dalton Transactions. 1999 ; No. 14. pp. 2393-2398.
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title = "A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S-C6H4)]- stabilized by S,S π-donation from chelating [S,S-C6H4]2-",
abstract = "The five-coordinate, sixteen-electron manganese(I) complex [N(PPh3)2][Mn(CO)3(S,S-C6H 4)] 1 was prepared from reaction of [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] and 1,2-benzenedithiol via the hexacoordinate intermediate fac-[Mn(CO)3(S-C6H4SH)(NH2,S-C 6H4)]-. Alternatively, oxidative addition of 1,2-benzenedithiol to [Mn(CO)5]-, followed by a Lewis acid-base reaction, with evolution of H2 gas (identified by gas chromatography), led to formation of the coordinatively-unsaturated complex 1. In contrast, reaction of bis(2-pyridyl) disulfide and [N(PPh3)2][Mn(CO)5] afforded hexacoordinate fac-[N(PPh3)2][Mn(CO)3(S-C5H 4-N)(S-C5H4N)] 2, with one anionic [S-C5H4N]- ligand bound to MnI in a monodentate (S-bonded) manner and the other [S-C5H4-N]- ligand bound in a bidentate manner (S,N-bonded). Complexes 1 and 2 have been characterized in solution by infrared spectroscopy and in the solid state by X-ray crystallography. The strong π-donating ability of the bidentate [S,S-C6H4]2- ligand stabilizes the unsaturated complex 1 which has short MnI-S bond lengths of 2.230(1) {\AA} (average) as a result. The existence of one π and two σ bonds between the [Mn(CO)3]+ and [S,S-C6H4]2- fragments, based on qualitative frontier molecular orbital analysis, also indicates that the lone-pair electrons are delocalized around the sulfur-manganese-sulfur system stabilizing the five-coordinate complex 1. The IR carbonyl stretching frequencies and the MnI-S bond distances of complexes 1 and [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] suggest that the relative π-donating ability of the bidentate ligands is [NH,S-C6H4]2- > [S,S-C6H4]2-. The Mulliken atomic charges derived from Hartree-Fock calculations roughly quantify the charge distribution in the complex [Mn(CO)3(NH,S-C6H4)]- (δ(N) = -1.14; δ(S) = -0.43; δ(Mn) = 1.14), and supports the premise that the reactions of [Mn(CO)3(NH,S-C6H4)]- with electrophiles (1,2-benzenedithiol, thiophene-2-thiol, 1,2-ethanedithiol) occur at the more electron-rich amide site, yielding charge-controlled, collision complexes.",
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A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S-C6H4)]- stabilized by S,S π-donation from chelating [S,S-C6H4]2-. / Lee, Chien Ming; Lin, Ging Yi; Hsieh, Chung Hung; Hu, Ching Han; Lee, Gene Hsiang; Peng, Shie Ming; Liaw, Wen Feng.

In: Journal of the Chemical Society - Dalton Transactions, No. 14, 21.07.1999, p. 2393-2398.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A five-coordinate, sixteen-electron manganese(I) complex [Mn(CO)3(S,S-C6H4)]- stabilized by S,S π-donation from chelating [S,S-C6H4]2-

AU - Lee, Chien Ming

AU - Lin, Ging Yi

AU - Hsieh, Chung Hung

AU - Hu, Ching Han

AU - Lee, Gene Hsiang

AU - Peng, Shie Ming

AU - Liaw, Wen Feng

PY - 1999/7/21

Y1 - 1999/7/21

N2 - The five-coordinate, sixteen-electron manganese(I) complex [N(PPh3)2][Mn(CO)3(S,S-C6H 4)] 1 was prepared from reaction of [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] and 1,2-benzenedithiol via the hexacoordinate intermediate fac-[Mn(CO)3(S-C6H4SH)(NH2,S-C 6H4)]-. Alternatively, oxidative addition of 1,2-benzenedithiol to [Mn(CO)5]-, followed by a Lewis acid-base reaction, with evolution of H2 gas (identified by gas chromatography), led to formation of the coordinatively-unsaturated complex 1. In contrast, reaction of bis(2-pyridyl) disulfide and [N(PPh3)2][Mn(CO)5] afforded hexacoordinate fac-[N(PPh3)2][Mn(CO)3(S-C5H 4-N)(S-C5H4N)] 2, with one anionic [S-C5H4N]- ligand bound to MnI in a monodentate (S-bonded) manner and the other [S-C5H4-N]- ligand bound in a bidentate manner (S,N-bonded). Complexes 1 and 2 have been characterized in solution by infrared spectroscopy and in the solid state by X-ray crystallography. The strong π-donating ability of the bidentate [S,S-C6H4]2- ligand stabilizes the unsaturated complex 1 which has short MnI-S bond lengths of 2.230(1) Å (average) as a result. The existence of one π and two σ bonds between the [Mn(CO)3]+ and [S,S-C6H4]2- fragments, based on qualitative frontier molecular orbital analysis, also indicates that the lone-pair electrons are delocalized around the sulfur-manganese-sulfur system stabilizing the five-coordinate complex 1. The IR carbonyl stretching frequencies and the MnI-S bond distances of complexes 1 and [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] suggest that the relative π-donating ability of the bidentate ligands is [NH,S-C6H4]2- > [S,S-C6H4]2-. The Mulliken atomic charges derived from Hartree-Fock calculations roughly quantify the charge distribution in the complex [Mn(CO)3(NH,S-C6H4)]- (δ(N) = -1.14; δ(S) = -0.43; δ(Mn) = 1.14), and supports the premise that the reactions of [Mn(CO)3(NH,S-C6H4)]- with electrophiles (1,2-benzenedithiol, thiophene-2-thiol, 1,2-ethanedithiol) occur at the more electron-rich amide site, yielding charge-controlled, collision complexes.

AB - The five-coordinate, sixteen-electron manganese(I) complex [N(PPh3)2][Mn(CO)3(S,S-C6H 4)] 1 was prepared from reaction of [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] and 1,2-benzenedithiol via the hexacoordinate intermediate fac-[Mn(CO)3(S-C6H4SH)(NH2,S-C 6H4)]-. Alternatively, oxidative addition of 1,2-benzenedithiol to [Mn(CO)5]-, followed by a Lewis acid-base reaction, with evolution of H2 gas (identified by gas chromatography), led to formation of the coordinatively-unsaturated complex 1. In contrast, reaction of bis(2-pyridyl) disulfide and [N(PPh3)2][Mn(CO)5] afforded hexacoordinate fac-[N(PPh3)2][Mn(CO)3(S-C5H 4-N)(S-C5H4N)] 2, with one anionic [S-C5H4N]- ligand bound to MnI in a monodentate (S-bonded) manner and the other [S-C5H4-N]- ligand bound in a bidentate manner (S,N-bonded). Complexes 1 and 2 have been characterized in solution by infrared spectroscopy and in the solid state by X-ray crystallography. The strong π-donating ability of the bidentate [S,S-C6H4]2- ligand stabilizes the unsaturated complex 1 which has short MnI-S bond lengths of 2.230(1) Å (average) as a result. The existence of one π and two σ bonds between the [Mn(CO)3]+ and [S,S-C6H4]2- fragments, based on qualitative frontier molecular orbital analysis, also indicates that the lone-pair electrons are delocalized around the sulfur-manganese-sulfur system stabilizing the five-coordinate complex 1. The IR carbonyl stretching frequencies and the MnI-S bond distances of complexes 1 and [N(PPh3)2][Mn(CO)3(NH,S-C6H 4)] suggest that the relative π-donating ability of the bidentate ligands is [NH,S-C6H4]2- > [S,S-C6H4]2-. The Mulliken atomic charges derived from Hartree-Fock calculations roughly quantify the charge distribution in the complex [Mn(CO)3(NH,S-C6H4)]- (δ(N) = -1.14; δ(S) = -0.43; δ(Mn) = 1.14), and supports the premise that the reactions of [Mn(CO)3(NH,S-C6H4)]- with electrophiles (1,2-benzenedithiol, thiophene-2-thiol, 1,2-ethanedithiol) occur at the more electron-rich amide site, yielding charge-controlled, collision complexes.

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