Platinum complexes containing or derived from olefinic phosphines P(X)((CH2)6CH=CH2)2 (X = OH, Ph, (CH2)6CH=CH2); ring closing metatheses, structures, and trans/cis isomerizations Academic Article uri icon

abstract

  • 2018 Elsevier Ltd The reaction of (O[dbnd])PH((CH 2 ) 6 CH[dbnd]CH 2 ) 2 (2.0 equiv) and PtCl 2 in toluene gives trans-PtCl 2 (P(OH)((CH 2 ) 6 CH[dbnd]CH 2 ) 2 ) 2 in 68% yield as a 82:18 mixture of PtClHOP hydrogen bond isomers. Addition of Grubbs first generation catalyst followed by hydrogenation (5 bar, cat. RhCl(PPh 3 ) 3 or PtO 2 ) affords the doubly trans spanning macrocyclic diphosphine adduct trans- [Figure presented] (319% crude yields). A crystal structure shows that the two OH groups are anti, and hydrogen bond to opposite ClPtCl chlorine atoms. The reaction of P(Ph)((CH 2 ) 6 CH[dbnd]CH 2 ) 2 (2.0 equiv) and PtCl 2 in toluene gives cis-PtCl 2 (P(Ph)((CH 2 ) 6 CH[dbnd]CH 2 ) 2 ) 2 (cis-5, 40%) and trans-5 (8%). The crystal structure of the former is determined. The trans/cis equilibrium ratios of these and related complexes are probed by DFT. Attempts to crystallize trans- [Figure presented] (trans-7), which is a minor product from a published metathesis/hydrogenation sequence involving trans-PtCl 2 (P((CH 2 ) 6 CH[dbnd]CH 2 ) 3 ) 2 , give only cis-7 as established by 31 P NMR and crystallography.

published proceedings

  • POLYHEDRON

altmetric score

  • 0.5

author list (cited authors)

  • Stollenz, M., Joshi, H., Ehnbom, A., Fiedler, T., Kharel, S., Reibenspies, J. H., ... Gladysz, J. A.

citation count

  • 2

complete list of authors

  • Stollenz, Michael||Joshi, Hemant||Ehnbom, Andreas||Fiedler, Tobias||Kharel, Sugam||Reibenspies, Joseph H||Bhuvanesh, Nattamai||Hall, Michael B||Gladysz, John A

publication date

  • January 2019