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- Title
A mixed-valent cyclodiphosphazane: Transition metal chemistry and cis/trans isomerisation.
- Authors
ANANTHNAG, GUDDEKOPPA; MAGUE, JOEL; BALAKRISHNA, MARAVANJI
- Abstract
The hydrolysis of cis-{ClP( μ-N Bu)P(NHBu)} ( 1) produced a mixed P/P derivative of cyclodiphosphazane, cis-{(BuNH)P( μ-N Bu)P(O)H} ( 2). The treatment of 2 with elemental selenium resulted in the formation of the monoselenide, trans-{(BuNH)P(Se)( μ-N Bu)P(O)H} ( 3) in good yield. The reactions of two equivalent of 2 with [Pd( μ-Cl)( η-C H)] or [Ru( η- p-cymene)( μ-Cl)Cl] in dichloromethane afforded corresponding mononuclear complexes, [( η-C H)PdCl{(BuNH)P( μ-N Bu)P(O)H}] ( 4) and [(( η- p-cymene)RuCl){(BuNH)P( μ-NBu)P(O)H}] ( 5). The treatment of 2 with M(COD)Cl (M = Pd and Pt) in dichloromethane at room temperature gave [MCl{(BuNH)P( μ-N Bu)P(O)H}] ( 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. [Figure not available: see fulltext.]
- Subjects
PHOSPHAZANES; VALENCE (Chemistry); TRANSITION metals; ISOMERIZATION; HYDROLYSIS; CYMENE
- Publication
Journal of Chemical Sciences, 2015, Vol 127, Issue 6, p979
- ISSN
0974-3626
- Publication type
Article
- DOI
10.1007/s12039-015-0865-3