Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene

Daniel L DuBois, Charles W. Eigenbrot, Alex Miedaner, James C. Smart, R. Curtis Haltiwanger

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Abstract

The synthesis of 1,1′-bis(diphenylphosphino)cobaltocene (1), (C5H4PPh2)2Co, from TlC5H4PPh2 and CoCl2 is described. The ligand 1 coordinates to one Mo(CO)4 fragment as a chelating bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)4] (2) and to two Mo(CO)5 fragments as a bridging bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)5]2 (3). Molecular structure determinations have been carried out on compounds 1 and 3. Compound 1 crystallizes in the monoclinic space group P21/c with cell dimensions a = 8.5966 (16) Å, b = 18.765 (4) Å, c = 8.8137 (15) Å, β = 99.702 (14)°, Z = 2, and ρ = 1.32 g cm-3. The structure was solved from 1735 observed reflections (F > 6σ(F)) and refined to final residuals of R = 0.033 and Rw = 0.041. Compound 3 crystallizes in the monoclinic space group C2/c with a = 16.651 (5) Å, b = 12.669 (6) Å, c = 26.322 (9) Å, β = 99.42 (2)°, Z = 4, and ρ = 1.47 g cm-3. The structure was solved from 1474 reflections (F > 6σ(F)) and refined to final residuals of R = 0.048 and Rw = 0.060. The puckering of the substituted cyclopentadienyl ring of 1 is interpreted with the aid of molecular orbital calculations. Cyclic voltammetry of 1 and Fe(C5H4PPh2)2 (4) and their complexes indicate that substitution of the cyclopentadienyl ring and coordination of 1 and 4 to molybdenum carbonyl fragments affects both the redox potential and electrochemical reversibility of electron-transfer processes occurring at cobalt and iron.

Original languageEnglish
Pages (from-to)1405-1411
Number of pages7
JournalOrganometallics
Volume5
Issue number7
Publication statusPublished - 1986

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Molybdenum
Carbon Monoxide
Molecular structure
molybdenum
molecular structure
fragments
ligands
synthesis
Ligands
rings
Orbital calculations
molecular orbitals
electron transfer
Molecular orbitals
cobalt
Chelation
Cobalt
substitutes
Cyclic voltammetry
iron

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

DuBois, D. L., Eigenbrot, C. W., Miedaner, A., Smart, J. C., & Haltiwanger, R. C. (1986). Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene. Organometallics, 5(7), 1405-1411.

Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene. / DuBois, Daniel L; Eigenbrot, Charles W.; Miedaner, Alex; Smart, James C.; Haltiwanger, R. Curtis.

In: Organometallics, Vol. 5, No. 7, 1986, p. 1405-1411.

Research output: Contribution to journalArticle

DuBois, DL, Eigenbrot, CW, Miedaner, A, Smart, JC & Haltiwanger, RC 1986, 'Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene', Organometallics, vol. 5, no. 7, pp. 1405-1411.
DuBois, Daniel L ; Eigenbrot, Charles W. ; Miedaner, Alex ; Smart, James C. ; Haltiwanger, R. Curtis. / Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene. In: Organometallics. 1986 ; Vol. 5, No. 7. pp. 1405-1411.
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abstract = "The synthesis of 1,1′-bis(diphenylphosphino)cobaltocene (1), (C5H4PPh2)2Co, from TlC5H4PPh2 and CoCl2 is described. The ligand 1 coordinates to one Mo(CO)4 fragment as a chelating bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)4] (2) and to two Mo(CO)5 fragments as a bridging bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)5]2 (3). Molecular structure determinations have been carried out on compounds 1 and 3. Compound 1 crystallizes in the monoclinic space group P21/c with cell dimensions a = 8.5966 (16) {\AA}, b = 18.765 (4) {\AA}, c = 8.8137 (15) {\AA}, β = 99.702 (14)°, Z = 2, and ρ = 1.32 g cm-3. The structure was solved from 1735 observed reflections (F > 6σ(F)) and refined to final residuals of R = 0.033 and Rw = 0.041. Compound 3 crystallizes in the monoclinic space group C2/c with a = 16.651 (5) {\AA}, b = 12.669 (6) {\AA}, c = 26.322 (9) {\AA}, β = 99.42 (2)°, Z = 4, and ρ = 1.47 g cm-3. The structure was solved from 1474 reflections (F > 6σ(F)) and refined to final residuals of R = 0.048 and Rw = 0.060. The puckering of the substituted cyclopentadienyl ring of 1 is interpreted with the aid of molecular orbital calculations. Cyclic voltammetry of 1 and Fe(C5H4PPh2)2 (4) and their complexes indicate that substitution of the cyclopentadienyl ring and coordination of 1 and 4 to molybdenum carbonyl fragments affects both the redox potential and electrochemical reversibility of electron-transfer processes occurring at cobalt and iron.",
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N2 - The synthesis of 1,1′-bis(diphenylphosphino)cobaltocene (1), (C5H4PPh2)2Co, from TlC5H4PPh2 and CoCl2 is described. The ligand 1 coordinates to one Mo(CO)4 fragment as a chelating bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)4] (2) and to two Mo(CO)5 fragments as a bridging bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)5]2 (3). Molecular structure determinations have been carried out on compounds 1 and 3. Compound 1 crystallizes in the monoclinic space group P21/c with cell dimensions a = 8.5966 (16) Å, b = 18.765 (4) Å, c = 8.8137 (15) Å, β = 99.702 (14)°, Z = 2, and ρ = 1.32 g cm-3. The structure was solved from 1735 observed reflections (F > 6σ(F)) and refined to final residuals of R = 0.033 and Rw = 0.041. Compound 3 crystallizes in the monoclinic space group C2/c with a = 16.651 (5) Å, b = 12.669 (6) Å, c = 26.322 (9) Å, β = 99.42 (2)°, Z = 4, and ρ = 1.47 g cm-3. The structure was solved from 1474 reflections (F > 6σ(F)) and refined to final residuals of R = 0.048 and Rw = 0.060. The puckering of the substituted cyclopentadienyl ring of 1 is interpreted with the aid of molecular orbital calculations. Cyclic voltammetry of 1 and Fe(C5H4PPh2)2 (4) and their complexes indicate that substitution of the cyclopentadienyl ring and coordination of 1 and 4 to molybdenum carbonyl fragments affects both the redox potential and electrochemical reversibility of electron-transfer processes occurring at cobalt and iron.

AB - The synthesis of 1,1′-bis(diphenylphosphino)cobaltocene (1), (C5H4PPh2)2Co, from TlC5H4PPh2 and CoCl2 is described. The ligand 1 coordinates to one Mo(CO)4 fragment as a chelating bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)4] (2) and to two Mo(CO)5 fragments as a bridging bidentate ligand to form [Co(C5H4PPh2)2] [Mo(CO)5]2 (3). Molecular structure determinations have been carried out on compounds 1 and 3. Compound 1 crystallizes in the monoclinic space group P21/c with cell dimensions a = 8.5966 (16) Å, b = 18.765 (4) Å, c = 8.8137 (15) Å, β = 99.702 (14)°, Z = 2, and ρ = 1.32 g cm-3. The structure was solved from 1735 observed reflections (F > 6σ(F)) and refined to final residuals of R = 0.033 and Rw = 0.041. Compound 3 crystallizes in the monoclinic space group C2/c with a = 16.651 (5) Å, b = 12.669 (6) Å, c = 26.322 (9) Å, β = 99.42 (2)°, Z = 4, and ρ = 1.47 g cm-3. The structure was solved from 1474 reflections (F > 6σ(F)) and refined to final residuals of R = 0.048 and Rw = 0.060. The puckering of the substituted cyclopentadienyl ring of 1 is interpreted with the aid of molecular orbital calculations. Cyclic voltammetry of 1 and Fe(C5H4PPh2)2 (4) and their complexes indicate that substitution of the cyclopentadienyl ring and coordination of 1 and 4 to molybdenum carbonyl fragments affects both the redox potential and electrochemical reversibility of electron-transfer processes occurring at cobalt and iron.

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