Syntheses of gyroscope-like molecules via three-fold ring closing metatheses of bis(phosphine) complexes trans-LyM(P((CH2)nCHCH2)3)2, and extensions to bis(phosphite) complexes trans-Fe(CO)3(P(O(CH2)nCHCH2)3)2 Conference Paper uri icon


  • The synthesis of trigonal bipyramidal, square planar, and octahedral bis(phosphine) complexes of the formula trans-LyM(P((CH2)nCH{double bond, long}CH2)3)2, and their conversion to gyroscope-like molecules trans-Ly{A figure is presented} via three-fold intramolecular alkene metathesis/hydrogenation sequences, is reviewed. New data involving bis(phosphite) complexes are then described. Reactions of P(NMe2)3 and HO(CH2)nCH{double bond, long}CH2 (n = a, 3; b, 4; c, 5; d, 6; e, 8; f, 9) afford the ligands P(O(CH2)nCH{double bond, long}CH2)3 (26a-f, 79-96%). Reactions of 26a,b,e,f and Fe(BDA)(CO)3 (BDA = benzylideneacetone) give trans-Fe(CO)3(P(O(CH2)nCH{double bond, long}CH2)3)2 (27a,b,e,f) as yellow or green oils in 17-64% yields after workup. Two representative complexes (27b,e) are treated with Grubbs' catalyst (2 × 6.5 mol%). NMR analyses of the resulting crude trans-Fe(CO)3(P(O(CH2)nCH{double bond, long}CH(CH2)nO)3P) (28b,e) suggest mixtures of Z/E isomers and perhaps oligomers. Subsequent ClRh(PPh3)3-catalyzed hydrogenations afford the title molecules trans{A figure is presented} (29b,e) as oils of 82-83% purity by 31P NMR. Although various properties of 29b,e can be compared to 27b,c, they could not be induced to solidify or crystallize, hampering purification. © 2007 Elsevier B.V. All rights reserved.

author list (cited authors)

  • Skopek, K., & Gladysz, J. A.

citation count

  • 44

publication date

  • March 2008