Abstract
Six extensive series of five-coordinate complexes of the types [Co(triphos)(CO)2]X and [Co(triphos)L(CO)]X (X = BF4, PF6; L = P(OMe)3, PPh2H, PPh2Me, PEt3, PPh3; triphos = either bis(3-diphenylphosphinopropyl)phenylphosphine (ttp), bis(2-diphenylphosphinoethyl)phenylphosphine (etp), or 1,1,1-tris(diphenylphosphinomethyl)ethane (tripod-P3)) were synthesized and their stereochemistry and dynamic behavior studied principally by 31P{1H} NMR. The details of the stereochemistry and exchange processes depend both on the monodentate ligand and on the triphosphine ligand. For example, the [Co(etp)L(CO)]X and [Co(etp)(CO)2]X complexes are trigonal bipyramidal with the equatorial positions occupied by a carbonyl ligand and the two terminal phosphorus atoms of the triphosphine ligand; the axial positions are occupied by the central phosphorus atom and either a monophosphine or a carbonyl ligand, respectively. The [Co(ttp)L(CO)]X complexes have square-pyramidal structures with L located at the axial position. A trigonal-bipyramidal structure is assigned to the dicarbonyl complexes [Co(ttp)(CO)2]X. The complexes [Co(tripod-P3)L(CO)]X are stereochemically nonrigid, whereas those of [Co(etp)L(CO)]X are stereochemically rigid at room temperature. A large number of 2JPP coupling constants are presented for these complexes.
| Original language | English |
|---|---|
| Pages (from-to) | 3076-3083 |
| Number of pages | 8 |
| Journal | Inorganic Chemistry |
| Volume | 15 |
| Issue number | 12 |
| Publication status | Published - 1976 |
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- Inorganic Chemistry
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Stereochemistry and exchange processes in five-coordinate cobalt(I) complexes containing one of three triphosphine ligands. / DuBois, Daniel L; Meek, Devon W.
In: Inorganic Chemistry, Vol. 15, No. 12, 1976, p. 3076-3083.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stereochemistry and exchange processes in five-coordinate cobalt(I) complexes containing one of three triphosphine ligands
AU - DuBois, Daniel L
AU - Meek, Devon W.
PY - 1976
Y1 - 1976
N2 - Six extensive series of five-coordinate complexes of the types [Co(triphos)(CO)2]X and [Co(triphos)L(CO)]X (X = BF4, PF6; L = P(OMe)3, PPh2H, PPh2Me, PEt3, PPh3; triphos = either bis(3-diphenylphosphinopropyl)phenylphosphine (ttp), bis(2-diphenylphosphinoethyl)phenylphosphine (etp), or 1,1,1-tris(diphenylphosphinomethyl)ethane (tripod-P3)) were synthesized and their stereochemistry and dynamic behavior studied principally by 31P{1H} NMR. The details of the stereochemistry and exchange processes depend both on the monodentate ligand and on the triphosphine ligand. For example, the [Co(etp)L(CO)]X and [Co(etp)(CO)2]X complexes are trigonal bipyramidal with the equatorial positions occupied by a carbonyl ligand and the two terminal phosphorus atoms of the triphosphine ligand; the axial positions are occupied by the central phosphorus atom and either a monophosphine or a carbonyl ligand, respectively. The [Co(ttp)L(CO)]X complexes have square-pyramidal structures with L located at the axial position. A trigonal-bipyramidal structure is assigned to the dicarbonyl complexes [Co(ttp)(CO)2]X. The complexes [Co(tripod-P3)L(CO)]X are stereochemically nonrigid, whereas those of [Co(etp)L(CO)]X are stereochemically rigid at room temperature. A large number of 2JPP coupling constants are presented for these complexes.
AB - Six extensive series of five-coordinate complexes of the types [Co(triphos)(CO)2]X and [Co(triphos)L(CO)]X (X = BF4, PF6; L = P(OMe)3, PPh2H, PPh2Me, PEt3, PPh3; triphos = either bis(3-diphenylphosphinopropyl)phenylphosphine (ttp), bis(2-diphenylphosphinoethyl)phenylphosphine (etp), or 1,1,1-tris(diphenylphosphinomethyl)ethane (tripod-P3)) were synthesized and their stereochemistry and dynamic behavior studied principally by 31P{1H} NMR. The details of the stereochemistry and exchange processes depend both on the monodentate ligand and on the triphosphine ligand. For example, the [Co(etp)L(CO)]X and [Co(etp)(CO)2]X complexes are trigonal bipyramidal with the equatorial positions occupied by a carbonyl ligand and the two terminal phosphorus atoms of the triphosphine ligand; the axial positions are occupied by the central phosphorus atom and either a monophosphine or a carbonyl ligand, respectively. The [Co(ttp)L(CO)]X complexes have square-pyramidal structures with L located at the axial position. A trigonal-bipyramidal structure is assigned to the dicarbonyl complexes [Co(ttp)(CO)2]X. The complexes [Co(tripod-P3)L(CO)]X are stereochemically nonrigid, whereas those of [Co(etp)L(CO)]X are stereochemically rigid at room temperature. A large number of 2JPP coupling constants are presented for these complexes.
UR - http://www.scopus.com/inward/record.url?scp=0000795366&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000795366&partnerID=8YFLogxK
M3 - Article
VL - 15
SP - 3076
EP - 3083
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 12
ER -