Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Quinquedentate Coordination of 10-Methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (L) to Rhodium(III). Crystal Structure of cis-[Rh(L)Cl][ClO4]2.H2O And Comparative Activation Volumes for Base Hydrolysis of [M(L)Cl]2+ (M = Rh, Co, Cr)

Quinquedentate Coordination of 10-Methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (L) to... <jats:p>The pendant-arm macrocycle 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (1) reacts slowly in hot water with rhodium(III) chloride to yield, following cation-exchange chromatography, exclusively cis -[ Rh (l) Cl ]2+. The cis -complex was crystallized readily as a perchlorate monohydrate salt, in the orthorhombic space group Pn21a, a 16.854(3), b 13.341(3), c 9.985(1) � , Z = 4, isomorphous with its cobalt(III) counterpart; a single-crystal X-ray structure determination was refined to R 0.027 for 1626 'observed' reflections. The pendant primary arnine and two adjacent secondary amines necessarily occupy an octahedral face, with the chloro ligand cis to the primary amine, and secondary amines adopt R,R,S,S stereochemistries. The Rh -N distances [2.056(6) � (pendant primary amine), average 2.08 � (secondary amines)], are at the short end of the range for Rh-N bonds. The Rh-Cl distance is 2.347(2) �. Activation volumes for chloride base hydrolysis were determined for cis -[ Rh (l) Cl ]2+as +19.5( � 1.2), for cis -[Co(l) Cl ]2+ as +27.1(�0.4), and for trans-[Cr(l) Cl ]2+ as +31.1( �0.1) cm3 mol-l, and are consistent with a conjugate base mechanism in each case; variations with metal ion are discussed.</jats:p> http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Australian Journal of Chemistry CrossRef

Quinquedentate Coordination of 10-Methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (L) to Rhodium(III). Crystal Structure of cis-[Rh(L)Cl][ClO4]2.H2O And Comparative Activation Volumes for Base Hydrolysis of [M(L)Cl]2+ (M = Rh, Co, Cr)

Australian Journal of Chemistry , Volume 45 (2): 351 – Jan 1, 1992

Quinquedentate Coordination of 10-Methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (L) to Rhodium(III). Crystal Structure of cis-[Rh(L)Cl][ClO4]2.H2O And Comparative Activation Volumes for Base Hydrolysis of [M(L)Cl]2+ (M = Rh, Co, Cr)


Abstract

<jats:p>The pendant-arm macrocycle 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (1) reacts slowly in hot water with rhodium(III) chloride to yield, following cation-exchange chromatography, exclusively cis -[ Rh (l) Cl ]2+.
The cis -complex was crystallized readily as a perchlorate monohydrate
salt, in the orthorhombic space group Pn21a, a 16.854(3), b
13.341(3), c 9.985(1) � , Z = 4, isomorphous with its cobalt(III) counterpart; a single-crystal X-ray structure determination was refined to R 0.027 for 1626 'observed' reflections. The pendant primary arnine and two adjacent secondary amines necessarily occupy an octahedral face, with the chloro
ligand cis to the primary amine, and secondary amines adopt R,R,S,S
stereochemistries. The Rh -N distances [2.056(6) � (pendant primary amine), average 2.08 � (secondary amines)], are at the short end of the range for Rh-N bonds. The Rh-Cl distance is 2.347(2) �. Activation volumes for chloride base hydrolysis were determined for cis -[ Rh (l) Cl ]2+as +19.5( � 1.2), for cis -[Co(l) Cl ]2+ as +27.1(�0.4), and for trans-[Cr(l) Cl ]2+ as +31.1( �0.1) cm3 mol-l, and are consistent with a conjugate base mechanism in each case; variations with metal ion are discussed.</jats:p>

Loading next page...
 
/lp/crossref/quinquedentate-coordination-of-10-methyl-1-4-8-12-EZ0NBc6s07

References

References for this paper are not available at this time. We will be adding them shortly, thank you for your patience.

Publisher
CrossRef
ISSN
0004-9425
DOI
10.1071/ch9920351
Publisher site
See Article on Publisher Site

Abstract

<jats:p>The pendant-arm macrocycle 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine (1) reacts slowly in hot water with rhodium(III) chloride to yield, following cation-exchange chromatography, exclusively cis -[ Rh (l) Cl ]2+. The cis -complex was crystallized readily as a perchlorate monohydrate salt, in the orthorhombic space group Pn21a, a 16.854(3), b 13.341(3), c 9.985(1) � , Z = 4, isomorphous with its cobalt(III) counterpart; a single-crystal X-ray structure determination was refined to R 0.027 for 1626 'observed' reflections. The pendant primary arnine and two adjacent secondary amines necessarily occupy an octahedral face, with the chloro ligand cis to the primary amine, and secondary amines adopt R,R,S,S stereochemistries. The Rh -N distances [2.056(6) � (pendant primary amine), average 2.08 � (secondary amines)], are at the short end of the range for Rh-N bonds. The Rh-Cl distance is 2.347(2) �. Activation volumes for chloride base hydrolysis were determined for cis -[ Rh (l) Cl ]2+as +19.5( � 1.2), for cis -[Co(l) Cl ]2+ as +27.1(�0.4), and for trans-[Cr(l) Cl ]2+ as +31.1( �0.1) cm3 mol-l, and are consistent with a conjugate base mechanism in each case; variations with metal ion are discussed.</jats:p>

Journal

Australian Journal of ChemistryCrossRef

Published: Jan 1, 1992

There are no references for this article.