title: Cyclic Aminophosphites and -phosphoranes Possessing Six- and Higher-Membered Rings: A Comparative Study of Structure and Reactivity.
abstract: Aminophosphoranes 2 and 4-9 with a cyclohexylamino substituent and ring sizes varying from five to eight have been synthesized by oxidative addition reactions of cyclic aminophosphites with diols or 1,2-diketones. The reactivities of these phosphoranes are compared with those of the corresponding cyclic aminophosphites. The difference in hydrolytic pathways between amino- and analogous phenoxyphosphoranes is discussed. X-ray structures of two sets of compounds, (a) (C(6)H(11)NH)P(OCH(2)CMe(2)CH(2)O) (1) and (C(6)H(11)NH)P(OCH(2)CMe(2)CH(2)O)(1,2-O(2)C(6)Cl(4)) (2) and (b) (C(6)H(11)NH)P{O-(t-Bu)(2)C(6)H(2))(2)CH(2)} (3) and (C(6)H(11)NH)P{(O-(t-Bu)(2)C(6)H(2))(2)CH(2)}(1,2-O(2)C(6)H(4)).(1)/(2)Et(2)O (4.(1)/(2)Et(2)O) have been determined and geometrical parameters compared between the P(III) and the corresponding P(V) compounds. In 1, the six-membered ring has a chair conformation with the amino group axial; in 2, the six-membered ring is located apical-equatorial in a trigonal bipyramidal geometry and has a boat conformation. The eight-membered ring has a boat-chair conformation in 3, whereas the same ring has a tub conformation in 4.
authors.affiliation: School of Chemistry, University of Hyderabad, Hyderabad-500046 A.P., India, and Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, D-37077 Göttingen, Germany.
authors.forename: Musa A.
authors.initials: MA
authors.lastname: Said
authors.forename: Melanie
authors.initials: M
authors.lastname: Pülm
authors.forename: R.
authors.initials: R
authors.lastname: Herbst-Irmer
authors.forename: K. C.
authors.initials: KC
authors.lastname: Kumara Swamy