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))ClO sub 4 , trans-CoLCl sub 2 , and cis-(CoL(CO sub 3 ))ClO sub 4
- Brookhaven National Lab., Upton, NY (USA)
The carbon monoxide adduct of the cobalt(I) title macrocycle has been prepared via reaction of CoL{sup +} with CO{sub 2} and with CO and isolated as a perchlorate salt: IR (Nujol){nu}{sub CO} 1916 cm{sup {minus}1}; UV-vis (CH{sub 3}CH, {lambda}{sub max} ({epsilon})) 310 nm (3900 M{sup {minus}1} cm{sup {minus}1}), 430 sh (770), 510 sh (360), 1040 (240). In CH{sub 3}CN solvent its stability constant is {approx} 3 {times} 10{sup 8} M{sup {minus}1} at 25{degree}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 K{alpha} radiation. Crystallographic data: (CoL(CO))(ClO{sub 4}) (1), C2, a = 15.362 (3) {angstrom}, b = 7.580 (5) {angstrom}, c = 9.611 (3) {angstrom}, {beta} = 108.91 (2){degree}, V = 1059 (1) {angstrom}{sup 3}, Z = 2 (R = 0.057, R{sub w} = 0.069); N-meso,trans-CoLCl{sub 2} (2), Pbca, a = 11.570 (3) {angstrom}, b = 12.695 (3) {angstrom}, c = 13.309 (2) {angstrom}, V = 1954 (1) {angstrom}{sup 3}, Z = 4 (R = 0.075, R{sub w} = 0.070); cis-(CoL(CO{sub 3}))ClO{sub 4} (3), C2, a = 15.072 (5) {angstrom}, b = 7.603 (4) {angstrom}, c = 9.703 (3) {angstrom}, {beta} = 109.74 (3){degree}, V = 1047 (1) {angstrom}{sup 3}, Z = 2 (R = 0.033, R{sub w} = 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. 30 refs., 3 figs., 8 tabs.
- DOE Contract Number:
- AC02-76CH00016
- OSTI ID:
- 5064161
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 28:8; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CRYSTAL STRUCTURE
COBALT COMPOUNDS
DIENES
ORGANIC NITROGEN COMPOUNDS
ORGANOMETALLIC COMPOUNDS
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
DATA
HYDROCARBONS
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYENES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties