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A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation

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Title A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation
 
Creator ANANTHNAG, GS
MAGUE, JT
BALAKRISHNA, MS
 
Subject X-RAY CRYSTAL
BIS(AMINO)CYCLODIPHOSPH(III)AZANE COMPLEXES
STRUCTURAL-CHARACTERIZATION
COORDINATION CHEMISTRY
COPPER(I) COORDINATION
ETHENE POLYMERIZATION
LIGANDS SYNTHESIS
P-COORDINATION
CIS
MACROCYCLE
Cyclodiphosphazanes
cis/trans isomerisation
NMR studies
complexes
 
Description The hydrolysis of cis-{ClP(mu-N (t) Bu)(2)P(NH (t) Bu)} (1) produced a mixed P-III/P (V) derivative of cyclodiphosphazane, cis-{( (t) BuNH)P(mu-N (t) Bu)(2)P(O)H} (2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{( (t) BuNH)P(Se)(mu-N (t) Bu)(2)P(O)H} (3) in good yield. The reactions of two equivalent of 2 with [Pd(mu-Cl)(eta (3)-C-3 H (5))](2) or [Ru(eta (6)-p-cymene)(mu-Cl)Cl](2) in dichloromethane afforded corresponding mononuclear complexes, [(eta (3)-C-3 H (5))PdCl{( (t) BuNH)P(mu-N (t) Bu)(2)P(O)H}] (4) and [((eta (6)-p-cymene)RuCl2){( (t) BuNH)P(mu-N (t) Bu)(2)P(O)H}] (5). The treatment of 2 with M(COD)Cl-2 (M = Pd and Pt) in dichloromethane at room temperature gave [MCl2{( (t) BuNH)P(mu-N (t) Bu)(2)P(O)H}(2)] (6 M = Pd; 7 M = Pt) in good yield. Owing to the cis/trans isomerisation of the cyclodiphosphazane rings, the complexes 6 and 7 exist as a mixture of two isomers. Various NMR spectroscopic techniques were employed for structural elucidation. The molecular structures of 5 and 7 were established by single crystal X-ray crystallographic studies.
 
Publisher INDIAN ACAD SCIENCES
 
Date 2016-01-14T12:33:19Z
2016-01-14T12:33:19Z
2015
 
Type Article
 
Identifier JOURNAL OF CHEMICAL SCIENCES, 127(6)979-986
0974-3626
0973-7103
http://dx.doi.org/10.1007/s12039-015-0865-3
http://dspace.library.iitb.ac.in/jspui/handle/100/17507
 
Language en