Record Details

Quaternization and oxidation reactions of cyclodiphosphazane derivatives and their copper(I) and gold(I) complexes

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title Quaternization and oxidation reactions of cyclodiphosphazane derivatives and their copper(I) and gold(I) complexes
 
Creator BALAKRISHNA, MS
SURESH, D
ANANTHNAG, GS
MAGUE, JT
 
Subject WATER-SOLUBLE PHOSPHINE
TRANSITION-METAL-COMPLEXES
X-RAY STRUCTURES
1,3,5-TRIAZA-7-PHOSPHAADAMANTANE PTA
ARYL BROMIDES
STRUCTURAL-CHARACTERIZATION
NEGATIVE HYPERCONJUGATION
DIALKYL AZODICARBOXYLATES
COORDINATION CHEMISTRY
MOLECULAR-STRUCTURES
 
Description The reactions of cyclodiphosphazane derivatives cis-{(BuN)-Bu-t(H)P(mu-(NBu)-Bu-t)(2)PN(H)Bu-t} (1), cis-{MeN(C4H8N)P( mu-(NBu)-Bu-t)(2)P(NC4H8Me)} (2) and {(Me2NCH2CH2O)P(mu-(NBu)-Bu-t)(2)P(OCH2CH2NMe2)} (3) with methyl iodide and methyl triflate and their subsequent reactions with elemental sulfur and selenium are reported. Interestingly, the reactions of 1-3 with an excess of methyl iodide resulted in quaternising only one phosphorus atom in cis-[{(BuNHP)-Bu-t(mu-(NBu)-Bu-t)(2)P(CH3)(NHBu)-Bu-t}](I) (4), two exocyclic nitrogen atoms and one of the phosphorus atoms in cis-{(Me2NC4H8N)P(mu-(NBu)-Bu-t)(2)P(CH3)(NC4H8NMe2)}](I)(3) (7) and only two exocyclic nitrogen atoms in cis-[{(Me3NCH2CH2O)P(mu-(NBu)-Bu-t)(2)P(OCH2CH2NMe3)}](I)(2) (8). The reaction of 1 with one equiv. of methyl triflate produced cis-[{(BuN)-Bu-t(H)P(mu-(NBu)-Bu-t)(2)P(CH3)N(H)Bu-t}]OTf (5), whereas the same reaction in a 1:2 molar ratio afforded cis-{(BuN)-Bu-t(H)P(CH3)(mu-(NBu)-Bu-t)(2)P(CH3)N(H)Bu-t}(OTf)(2) (6). Compounds 4 and 5 showed poor solubility in water, whereas 7 and 8 were high melting crystalline solids with moderate to good water solubility. Treatment of 4 with either elemental sulfur or selenium gave both cis- and transchalcogenide derivatives. Similar reactions of 7 and 8 produced both mono-and bischalcogenides. Reactions between 4 or 7 and CuI yielded dinuclear complexes, cis-[{Cu-2(mu-I)(3)((BuN)-Bu-t(H)P)(mu-NtBu) 2( P(CH3)N( H)Bu-t)]2}(I)] (15) and cis-[{Cu-2(mu-I)(3)[(Me2NC4H8N)P(mu-(NBu)-Bu-t)(2)P(CH3)(NC4H8NMe2)] 2}(I)(5)] (16), while the reaction of 8 with CuI produced a coordination polymer [{Cu2(mu-I)3(mu-(NBuP)-Bu-t)(2)(OCH2CH2NMe3)(2)}I](8) (17), containing triiodo-bridged [Cu-2(mu-I)(3)] linkers. The molecular structures of several of these compounds were confirmed by single crystal X-ray diffraction studies. The Cu-vertical bar...Cu-vertical bar distance of 2.55 angstrom in 15 is quite short and is the same as that found in copper metal and also in complexes containing [Cu-2(mu-I)(3)] linkers. All the metal complexes exhibit strong intra-, inter- or both intra- and inter-molecular hydrogen bonding interactions.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-12-28T12:15:49Z
2014-12-28T12:15:49Z
2014
 
Type Article
 
Identifier DALTON TRANSACTIONS, 43(23)8835-8848
1477-9226
1477-9234
http://dx.doi.org/10.1039/c4dt00801d
http://dspace.library.iitb.ac.in/jspui/handle/100/16475
 
Language English