Structurally diverse penta- and hexacoordinate phosphorus compounds from the reaction of diethyl or diisopropyl azodicarboxylates with phosphorus(iii) compounds†
Abstract
The reaction of C(OR)O–] [R = Et (21a), i-Pr (21b)]. Treatment of 21a–b with
C(OR)O–] [NRR′ = pyrazolyl (12a–b),
C(OR)O–] (15), but S(6-t-Bu-4-Me–C6H2O)2PCl (20a) gives the hexacoordinate phosphorane S(6-t-Bu-4-Me–C6H2O)2PCl[N(COOR)–N
C(OR)O–] (16) with the shortest known S→P coordinate bond. Compound 15 also exhibits the ‘reversed apicophilicity’ phenomenon, but the disposition of substituents is different from that in 12–13. The compound S(6-t-Bu-4-Me–C6H2O)2PPh[N(COOR)–N
C(OR)O–] (17) is prepared similarly. Reaction of 16 with
C(OR)O–] (18). Both 17 and 18 show distorted octahedral geometry with S→P coordination, but the sulfur is trans to the