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

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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 2014-12-28T12:18:45Z
2014-12-28T12:18:45Z
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/100/16486
 
Language English