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Alkyl‐Tethered Bis‐Phosphoryl Compounds with two 1,3,2‐Benzodiazaphosphorinone Units; Oxidation, Complexation, and X‐Ray Structure Analysis of Selected Compounds
Author(s) -
Fei Zhaofu,
Thönnessen Holger,
Jones Peter G.,
Crowe Lindsey,
Harris Robin K.,
Schmutzler Reinhard
Publication year - 2000
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 - 10.1002/1521-3749(200008)626:8<1763::aid-zaac1763>3.0.co;2-u
Subject(s) - chemistry , nmr spectra database , adduct , triethylamine , medicinal chemistry , nuclear magnetic resonance spectroscopy , amine gas treating , crystallography , alkyl , stereochemistry , spectral line , organic chemistry , physics , astronomy
The reaction of the bis‐chlorophosphines 1 a – 1 d with bis(2‐chloroethyl)amine hydrochloride in the presence of triethylamine and with various trimethylsilylamines led to a new class of bis‐phosphorus ligands 2 a – 2 c and 3 a – 3 g . 31 P‐NMR studies suggested that the bis‐phosphorus ligands undergo rotation reactions about the alkyl bridge in polar solvents. Compounds 2 a – 2 c showed initially only one sharp singlet each in their 31 P‐NMR spectra. After a few days at room temperature, two signals were observed. Similar results were observed for 3 a – 3 g . In the solid state, the two phosphorus atoms in 2 c are not equivalent, as was confirmed by the observation of two signals in the solid state 31 P‐NMR spectrum. Oxidation reactions of 2 a – 2 c by the hydrogen peroxide‐urea 1 : 1 adduct (NH 2 ) 2 C(:O) · H 2 O 2 led to the formation of the corresponding phosphoryl compounds 4 a – 4 c . Reaction of 2 a and 3 a with Pt[COD]Cl 2 (COD = 1.5‐Cyclooctadiene) furnished the complexes 5 and 6 . The NMR spectra suggested that the two chlorine atoms are in cis position. X‐ray structure analyses were conducted for 2 a , which exhibits twofold symmetry; 2 c , which is linked into dimers by hydrogen bonds C–H…O; and 6 , confirming the cis configuration.