NDLI: π-Excess $σ^{2}P$ ligands: synthesis of biaryl-type 1,3-benzazaphosphole hybrid ligands and formation of $P\^P′–M(CO)

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Heinicke, Joachim W. Jones, Peter G. Ghalib, Mohammed Niaz, Basit
Description	Author Affiliation: Niaz B ( Institut für Biochemie, Anorganische Chemie, Ernst-Moritz-Arndt-Universität Greifswald, Felix-Hausdorff-Str. 4, D-17489 Greifswald, Germany.)
Abstract	Acid-catalyzed cyclocondensations of 2-phosphanylanilines 1 with substituted benzaldehydes or heteroaryl aldehydes open a convenient route to new biaryl-type 1H-1,3-benzazaphosphole hybrid ligands 2a–f with o-phosphanylphenyl, pyridyl, imidazolyl, thienyl or o-methoxyphenyl donor groups (in addition to the $σ^{2}P$ donor) and to bromophenyl substituted benzazaphospholes 2g,h. Excess aldehyde leads to concomitant reductive N-alkylation, as shown by formation of 3h besides 2h. The reactions proceed via dihydrobenzazaphospholes 4, which can be detected under mild conditions. The aromaticity-driven dehydrogenation does not liberate dihydrogen but is accomplished by transfer hydrogenations, mainly by reduction of some of the aldehyde. N-Secondary 2-phosphanylanilines 5 also react with aldehydes to form the corresponding N-substituted benzazaphospholes 6. The formation of $(P\^P′)M(CO)_{4}-chelate$ complexes 8a (M = Cr) and 9a,b (M = Mo) was demonstrated by reaction with $M(CO)_{4}(norbornadiene).$ The crystal structure of 9a, determined in addition to the solution structure elucidation by multinuclear NMR spectra, confirms the chelate formation and reveals a trigonal environment for the low coordinated phosphorus, with the P–Mo(0) vector bent out of the benzazaphosphole ring plane by 14.4° (0.57 Å), together with axial chirality of the molecules in the racemic crystals by twisting of the benzazaphosphole and phenyl π-planes around the common C(2)–C(21) bond.
ISSN	14779226
Issue Number	26
Volume Number	42
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-07-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Aza Compounds Chemical Synthesis Carbon Monoxide Chemistry Chelating Agents Chromium Coordination Complexes Phosphorus Ligands Models, Molecular Molecular Structure Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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