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 language | English |
|---|---|
| Pages (from-to) | 1405-1411 |
| Number of pages | 7 |
| Journal | Organometallics |
| Volume | 5 |
| Issue number | 7 |
| Publication status | Published - 1986 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
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 journal › Article
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TY - JOUR
T1 - Synthesis, molecular structure, and molybdenum complexes of 1,1′-bis(diphenylphosphino)cobaltocene
AU - DuBois, Daniel L
AU - Eigenbrot, Charles W.
AU - Miedaner, Alex
AU - Smart, James C.
AU - Haltiwanger, R. Curtis
PY - 1986
Y1 - 1986
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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UR - http://www.scopus.com/inward/citedby.url?scp=0000111640&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0000111640
VL - 5
SP - 1405
EP - 1411
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 7
ER -