N-chlorotriphenylphosphaneimine and its application as an educt for the synthesis of asymmetric PNP cations. Crystal structures of Ph3PNCl and [Ph3PNPEt3]Cl

Ph3PNCl (1) originates in good yield as pale yellow crystals from the react ion of Ph3PNSiMe3 with phenyl-iodine dichloride. According to the crystal s tructure analysis 1 has a monomeric molecular structure without perceptible intermolecular contacts with distances P-N of 161.0 pm, N-Cl of 175.9 pm, and with a PNCl bond angle of 110.31 degrees. 1 reacts with phosphines PR3 forming asymmetric PNP salts [Ph3PNPR3]Cl. This was tested by reactions wit h PEt3 and bis-diphenyl phosphano ferrocene (DPPF). The crystal structure a nalysis of [Ph3PNPEt3]Cl (2) shows an almost symmetric PNP bridge with dist ances PN of 158.6 and 157.0 pm, and with a bond angle of 145.9 degrees.