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

David J. Szalda, Etsuko Fujita, Carol Creutz

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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 languageEnglish
Pages (from-to)1446-1450
Number of pages5
JournalInorganic Chemistry
Volume28
Issue number8
Publication statusPublished - 1989

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dienes
Cobalt
Molecular structure
molecular structure
cobalt
Crystal structure
crystal structure
Carbon Monoxide
perchlorates
coordination number
carbon monoxide
adducts
Salts
Single crystals
salts
Radiation
X ray diffraction
Oxidation
oxidation
perchlorate

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{59b9044485a34751bd93541682f7e2ac,
title = "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",
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) {\AA}, b = 7.580 (5) {\AA}, c = 9.611 (3) {\AA}, β = 108.91 (2)°, V = 1059 (1) {\AA}3, Z = 2 (R = 0.057, Rw = 0.069); N-meso,trans-CoLCl2 (2), Pbca, a = 11.570 (3) {\AA}, b = 12.695 (3) {\AA}, c = 13.309 (2) {\AA}, V = 1954 (1) {\AA}3, Z = 4 (R = 0.075, Rw = 0.070); cis-[CoL(CO3)]ClO4 (3), C2, a = 15.072 (5) {\AA}, b = 7.603 (4) {\AA}, c = 9.703 (3) {\AA}, β = 109.74 (3)°, V = 1047 (1) {\AA}3, 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.",
author = "Szalda, {David J.} and Etsuko Fujita and Carol Creutz",
year = "1989",
language = "English",
volume = "28",
pages = "1446--1450",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "8",

}

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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