title: Selection of the cis and trans phosph(III)azane macrocycles [{P(mu-NtBu)}2(1-Y-2-NH-C6H4)]2(Y=O, S).
abstract: The 1 : 1 reactions of [ClP(mu-NtBu)]2 with the difunctional aromatic amines 1,2-1-YH-2-NH2-C6H4 in the presence of Et3N give the dimeric phosph(III)azane macrocycles [{P(mu-NtBu)2(1-Y-2-HN-C6H4)]2, predominantly as the cis isomer in the case of Y=O (1.cis) and as the trans isomer for Y=S (2.trans). Model M.O. calculations suggest that the selection of the cis and trans isomers is not thermodynamically controlled. The alternative isomers 1.trans and 2.cis are generated exclusively by the deprotonation of the model intermediates [(1-Y-2-NH2-C6H4)P(mu-NtBu)]2[Y=O (3), S (4)] with nBuLi followed by cyclisation with [ClP(mu-NtBu)]2. The solid-state structures of 1.cis/trans(50 : 50), 2.cis, 3 and 4 are reported.
authors.affiliation: Chemistry Department, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW. dsw1000@cus.cam.ac.uk.
authors.forename: Felipe
authors.initials: F
authors.lastname: Garcia
authors.forename: Jonathan M
authors.initials: JM
authors.lastname: Goodman
authors.forename: Richard A
authors.initials: RA
authors.lastname: Kowenicki
authors.forename: Mary
authors.initials: M
authors.lastname: McPartlin
authors.forename: Lucia
authors.initials: L
authors.lastname: Riera
authors.forename: Maria A
authors.initials: MA
authors.lastname: Silva
authors.forename: Andreas
authors.initials: A
authors.lastname: Wirsing
authors.forename: Dominic S
authors.initials: DS
authors.lastname: Wright
mesh_terms: D018360:Crystallography, X-Ray; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009943:Organophosphorus Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
chemical_list: D047028:Macrocyclic Compounds; D009943:Organophosphorus Compounds