Abstract
Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).
| Original language | English |
|---|---|
| Pages (from-to) | 391-395 |
| Number of pages | 5 |
| Journal | Organometallics |
| Volume | 8 |
| Issue number | 2 |
| State | Published - 1989 |
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All Science Journal Classification (ASJC) codes
- Inorganic Chemistry
- Organic Chemistry
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2-[Bis(diphenylphosphino)methyl]pyridine (PNP) derivatives of rhenium carbonyl. Crystal and molecular structure of Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 . / Mattson, Bruce M.; Ito, Larry N.
In: Organometallics, Vol. 8, No. 2, 1989, p. 391-395.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - 2-[Bis(diphenylphosphino)methyl]pyridine (PNP) derivatives of rhenium carbonyl. Crystal and molecular structure of Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7
AU - Mattson, Bruce M.
AU - Ito, Larry N.
PY - 1989
Y1 - 1989
N2 - Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).
AB - Two new 2-[bis(diphenylphosphino)methyl]pyridine (PNP) complexes of rhenium have been synthesized. Re2(η2,η2-PNP)(CO)8 was synthesized from Re2(CO)8(μ-H)(μ-CH=CHC4H9) and an excess of PNP in CH2Cl2 solution. Re2(η2,η2-PNP)(CO)8 was characterized by IR, mass, and 1H, 31P, and 13C NMR spectroscopies. The structure of Re2(η2,η2-PNP)(CO)8 is based on Re2(CO)10 in which one eq-CO on each Re has been replaced with phosphino groups from the bridging PNP ligand. The pyridyl group is not coordinated. Re2(η2,η2-PNP)(CO)8 thermally decarbonylates in toluene solution to afford Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C6H4N)(CO)7 in high yield. Re2(μ-PPh2)(μ-η1,η 4-CHPPh2C5H4N)(CO)7 was characterized spectroscopically and by a single-crystal X-ray diffraction [P, a = 10.906 (10) Å, b = 18.164 (9) Å, c = 10.973 (6) Å, α = 98.56 (5)°, β = 119.12 (6)°, γ = 94.14 (8)°, Z = 2, D = 1.951 g cm-3, R = 0.045]. The molecular structure was found to consist of two octahedral rhenium centers joined by a μ-PPh2 ligand and a μ-C5H4NCHPPh2 (PN) moiety. These two bridges are the fragments that result when the coordinated PNP in Re2(η2,η2-PNP)(CO)8 undergoes P-C bond activation. The PN group chelates in a bidentate manner to one Re and is σ-bonded via the methine C to the other Re. No Re-Re bond exists (4.189 Å).
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M3 - Article
VL - 8
SP - 391
EP - 395
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 2
ER -