GROUP 15-AZAMACROCYCLIC CHEMISTRY - REACTIONS OF 1,4,8,11-TETRAMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE-(L) WITH MCL3 (M = AS OR SB) - CRYSTAL AND MOLECULAR-STRUCTURES OF [H2L][AS4O2CL10] AND [H2L][SB2OCL6]
UNSPECIFIED. (1993) GROUP 15-AZAMACROCYCLIC CHEMISTRY - REACTIONS OF 1,4,8,11-TETRAMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE-(L) WITH MCL3 (M = AS OR SB) - CRYSTAL AND MOLECULAR-STRUCTURES OF [H2L][AS4O2CL10] AND [H2L][SB2OCL6]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (3). pp. 365-370. ISSN 0300-9246Full text not available from this repository.
The reactions of MCl3 (M = As or Sb) and 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (tetramethylcyclam, L) have been studied under controlled hydrolysis conditions as a routs to anionic bridging chlorooxo arsenic- or antimony- (III) species. With M = As, the ionic complex [H2L][As4O2Cl10] 1 has been isolated and characterised by an X-ray crystal-structure determination. The diprotonated tetraazamacrocyclic dications adopt an endodentate geometry with all four N-CH3 groups positioned on the same side of the ring in an R,S,R,S [trans-(I)] configuration. The two protons are bonded to alternate nitrogen atoms and are involved in hydrogen bonding within the ring cavity. Each arsenic(III) centre of the tetranuclear mu4-chloro-mu-oxo complex anion (As4O2Cl10]2- shows psi-octahedral co-ordination geometry with an associated stereochemically active lone pair. With M = Sb, the ionic complex [H2L][Sb2OCl6] 2 has been isolated and its structure determined. The macrocyclic dications are again in an endodentate conformation with intramolecular hydrogen bonding across the ring cavity but in this-case the N-CH3 groups are directed in pairs to opposite sides of the ring in an R,R,S,S [trans-(III)] configuration. The antimony atoms of the binuclear mu-chloro-mu-oxo complex anion [Sb2OCl6]2- have psi-octahedral geometry with a stereochemically active lone pair. Both anions contain similar Cl2MOMCl2 Primary units (mean As-Cl 2.21, Sb-Cl 2.43, As-O 1.77, Sb-O 1.94 angstrom) with Cl- ions forming secondary M ... Cl interactions (mean As ... Cl 3.08, Sb ... Cl 2.89 angstrom).
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Journal or Publication Title:||JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS|
|Publisher:||ROYAL SOC CHEMISTRY|
|Official Date:||7 February 1993|
|Number of Pages:||6|
|Page Range:||pp. 365-370|
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