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Synthesis of Ethylene‐bridged Heterocyclic Bidentate P(III)N‐Ligands — Oxidation and Complexation Studies
Author(s) -
Lu Yingzi,
Freytag Matthias,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300186
Subject(s) - conformational isomerism , chemistry , denticity , ethylene , nmr spectra database , crystallography , tetrazole , crystal structure , singlet state , hexafluoroacetone , derivative (finance) , stereochemistry , medicinal chemistry , spectral line , molecule , catalysis , organic chemistry , physics , astronomy , nuclear physics , financial economics , economics , excited state
A series of phosphor(III)inanone ligands 4‐7 , linked by ethylene bridges between the nitrogen atoms of the heterocyclic rings, were synthesized by the reaction of the bis‐PCl derivative 3 with the appropriate trimethylsilylamines. The bis‐phosphor(V)inanone compounds 8‐11 were obtained by the oxidation of 4‐7 with hexafluoroacetone (HFA). Oxidation of 4 and 6 with tetrachloro‐orthobenzoquinone (TOB) gave the bis‐phosphor(V)inanones 12 and 13 . The reaction of 4‐6 with [Pt(COD)Cl 2 ] led to the platinum complexes 14‐16 . All the σ 3 ‐phosphorinanone compounds 4‐7 and the σ 5 ‐phosphorinanone compounds 8‐10 , 12 and 13 exist as a mixture of two conformers, as indicated by two signals in the 31 P‐NMR spectra. However, compounds 9 and 11 exist as single conformers, both display only one sharp singlet in the 31 P‐NMR spectra. The Pt‐complexes 15 and 16 contain two conformers; one conformer of 16 could be isolated by crystallization. X‐ray crystal structure determinations for compounds 8 , 14 and 16 were conducted, revealing inversion symmetry for 8 and cis arrangement for 14 and 16 .