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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))ClO sub 4 , trans-CoLCl sub 2 , and cis-(CoL(CO sub 3 ))ClO sub 4

Abstract

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} =more » 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.« less

Authors:
; ;  [1]
  1. Brookhaven National Lab., Upton, NY (USA)
Publication Date:
OSTI Identifier:
5064161
DOE Contract Number:  
AC02-76CH00016
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 28:8; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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

Citation Formats

Szalda, D J, Fujita, E, and Creutz, C. 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. United States: N. p., 1989. Web. doi:10.1021/ic00307a006.
Szalda, D J, Fujita, E, & Creutz, C. 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. United States. doi:10.1021/ic00307a006.
Szalda, D J, Fujita, E, and Creutz, C. Wed . "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". United States. doi:10.1021/ic00307a006.
@article{osti_5064161,
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))ClO sub 4 , trans-CoLCl sub 2 , and cis-(CoL(CO sub 3 ))ClO sub 4},
author = {Szalda, D J and Fujita, E and Creutz, C},
abstractNote = {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.},
doi = {10.1021/ic00307a006},
journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 28:8,
place = {United States},
year = {1989},
month = {4}
}