Abstract
The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL+ with CO2 and with CO and isolated as a perchlorate salt: IR (Nujol) vCO 1916 cm-1; UV-vis (CH3CN, λmax (ε)) 310 nm (3900 M-1 cm-1), 430 sh (770), 510 sh (360), 1040 (240). In CH3CN solvent its stability constant is ∼3 × 108 M-1 at 25°C. Structures of the square-pyramidal carbonyl complex and two other complexes of the title macrocycle have been determined from single-crystal X-ray diffraction data collected with use of Mo Ka radiation. Crystallographic data: [CoL(CO)](ClO4) (1), C2, a = 15.362 (3) Å, b = 7.580 (5) Å, c = 9.611 (3) Å, β = 108.91 (2)°, V = 1059 (1) Å3, Z = 2 (R = 0.057, Rw = 0.069); N-meso,trans-CoLCl2 (2), Pbca, a = 11.570 (3) Å, b = 12.695 (3) Å, c = 13.309 (2) Å, V = 1954 (1) Å3, Z = 4 (R = 0.075, Rw = 0.070); cis-[CoL(CO3)]ClO4 (3), C2, a = 15.072 (5) Å, b = 7.603 (4) Å, c = 9.703 (3) Å, β = 109.74 (3)°, V = 1047 (1) Å3, Z = 2 (R = 0.033, Rw = 0.048). The three structures contain square-pyramidal, five-coordinate cobalt(I) (1), strongly axially distorted "six"-coordinate cobalt(II) (2), and six-coordinate cobalt(III) with L occupying cis-coordination positions (3). They thus provide a striking illustration of the adaptability of L to a variety of coordination numbers and oxidation states.
| Original language | English |
|---|---|
| Pages (from-to) | 1446-1450 |
| Number of pages | 5 |
| Journal | Inorganic Chemistry |
| Volume | 28 |
| Issue number | 8 |
| Publication status | Published - 1989 |
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- Inorganic Chemistry
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Cobalt(I), -(II), and -(III) complexes of a tetraaza 14-membered macrocycle, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (L). Crystal and molecular structures of [CoL(CO)]ClO4, trans-CoLCl2, and cis-[CoL(CO3)]ClO4 . / Szalda, David J.; Fujita, Etsuko; Creutz, Carol.
In: Inorganic Chemistry, Vol. 28, No. 8, 1989, p. 1446-1450.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Cobalt(I), -(II), and -(III) complexes of a tetraaza 14-membered macrocycle, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (L). Crystal and molecular structures of [CoL(CO)]ClO4, trans-CoLCl2, and cis-[CoL(CO3)]ClO4
AU - Szalda, David J.
AU - Fujita, Etsuko
AU - Creutz, Carol
PY - 1989
Y1 - 1989
N2 - The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL+ with CO2 and with CO and isolated as a perchlorate salt: IR (Nujol) vCO 1916 cm-1; UV-vis (CH3CN, λmax (ε)) 310 nm (3900 M-1 cm-1), 430 sh (770), 510 sh (360), 1040 (240). In CH3CN solvent its stability constant is ∼3 × 108 M-1 at 25°C. Structures of the square-pyramidal carbonyl complex and two other complexes of the title macrocycle have been determined from single-crystal X-ray diffraction data collected with use of Mo Ka radiation. Crystallographic data: [CoL(CO)](ClO4) (1), C2, a = 15.362 (3) Å, b = 7.580 (5) Å, c = 9.611 (3) Å, β = 108.91 (2)°, V = 1059 (1) Å3, Z = 2 (R = 0.057, Rw = 0.069); N-meso,trans-CoLCl2 (2), Pbca, a = 11.570 (3) Å, b = 12.695 (3) Å, c = 13.309 (2) Å, V = 1954 (1) Å3, Z = 4 (R = 0.075, Rw = 0.070); cis-[CoL(CO3)]ClO4 (3), C2, a = 15.072 (5) Å, b = 7.603 (4) Å, c = 9.703 (3) Å, β = 109.74 (3)°, V = 1047 (1) Å3, Z = 2 (R = 0.033, Rw = 0.048). The three structures contain square-pyramidal, five-coordinate cobalt(I) (1), strongly axially distorted "six"-coordinate cobalt(II) (2), and six-coordinate cobalt(III) with L occupying cis-coordination positions (3). They thus provide a striking illustration of the adaptability of L to a variety of coordination numbers and oxidation states.
AB - The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL+ with CO2 and with CO and isolated as a perchlorate salt: IR (Nujol) vCO 1916 cm-1; UV-vis (CH3CN, λmax (ε)) 310 nm (3900 M-1 cm-1), 430 sh (770), 510 sh (360), 1040 (240). In CH3CN solvent its stability constant is ∼3 × 108 M-1 at 25°C. Structures of the square-pyramidal carbonyl complex and two other complexes of the title macrocycle have been determined from single-crystal X-ray diffraction data collected with use of Mo Ka radiation. Crystallographic data: [CoL(CO)](ClO4) (1), C2, a = 15.362 (3) Å, b = 7.580 (5) Å, c = 9.611 (3) Å, β = 108.91 (2)°, V = 1059 (1) Å3, Z = 2 (R = 0.057, Rw = 0.069); N-meso,trans-CoLCl2 (2), Pbca, a = 11.570 (3) Å, b = 12.695 (3) Å, c = 13.309 (2) Å, V = 1954 (1) Å3, Z = 4 (R = 0.075, Rw = 0.070); cis-[CoL(CO3)]ClO4 (3), C2, a = 15.072 (5) Å, b = 7.603 (4) Å, c = 9.703 (3) Å, β = 109.74 (3)°, V = 1047 (1) Å3, Z = 2 (R = 0.033, Rw = 0.048). The three structures contain square-pyramidal, five-coordinate cobalt(I) (1), strongly axially distorted "six"-coordinate cobalt(II) (2), and six-coordinate cobalt(III) with L occupying cis-coordination positions (3). They thus provide a striking illustration of the adaptability of L to a variety of coordination numbers and oxidation states.
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M3 - Article
VL - 28
SP - 1446
EP - 1450
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 8
ER -