An Optically Active Carbodiimide

✍ Scribed by Prof. K. Schlögl; H. Mechtler

• Publisher: John Wiley and Sons
• Year: 1966
• Tongue: English
• Weight: 128 KB
• Volume: 5
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.196605961

✦ Synopsis

factory'"21 equation (b) (r = 0.965); of the three a-values (see table) determined for phosphorus-containing substituents with this equation, those of the p-diphenylphosphino and diphenylphosphhyl groups agree well with the constants derived from the p K a values of the acids. Phosphorus behaves throughout as an electron acceptor, the order being phosphonium-> phosphinylw thiophosphinyl-> phosphine-phosphorus. (C,&5)2P(O) has apara only slightly greater than ameta = +0.485 determined by alkaline cleavage of 3-(dipheny1phosphinyl)benzyltrimethylsilane [a; thus in this case 3d-orbital participation appears not to be significant. However, the fact that G ( C ~H ~) ~P < G ( C ~H ~) ~P ( O ) -as in the phosphine p-(C6H5)2P-C&-N(CH3)2[31indicates a certain amount of 3p-orbital participation by the phosphine-phosphorus. X 6.09 5.74 5.50 5.34 4.97 4.94 4.38 4.