SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE THIOFORMALDEHYDE COMPLEX [(ETA-5-C5H5)RE(NO)(PPH3)(ETA-2-H2C=S)]+PF6- Academic Article uri icon

abstract

  • Reaction of [(75-C5H5)Re(NO)(PPh3)(=CH2)]+PF6 (2) and S=PPh3gives a 1:1 mixture of thioformaldehyde complex [(-C5H5)Re(NO)(PPh3)(2-H2C=S)]+PF6 (1) and ylide complex [5-C5H5)Re-(NO)(PPh3)(CH2PPh3)]+PF6~ (3). However, reaction of 2 and cyclohexene sulfide gives 1 (85-95% after recrystallization). An X-ray structure of 1 (crystal data: monoclinic, P2i/c; a = 9.688 (2) A, b = 18.536 (4) A, c = 14.895 (s) A; = 103.53 (2); Z = 4) shows that the 2-H2C=S ligand adopts a conformation that has significant overlap of its * orbital with the rhenium fragment HOMO and its sulfur terminus syn to the PPh3. Extended Huckel MO calculations on the model compound [5-C5H5)Re(NO)-(PH3)(2-H2C=S)]+predict a similar conformational energy minimum. Complex 1 is stable in CD3CN (41 h, 51 C) but rapidly reacts with PPh3(2 equiv) to give 3 (95%) and SPPh3(88%). Reaction of 1 and NaBH3CN gives thiomethyl complex (5-C5H5)Re(NO)(PPh3)(SCH3) (5, 85% after recrystallization). The reactivity of 1 is compared to that of formaldehyde complex [(5-C5H5)Re(N0)(PPh3)(2-H2C=0)]+PF6~, and the mechanisms of the above reactions are discussed. 1987, American Chemical Society. All rights reserved.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • BUHRO, W. E., ETTER, M. C., GEORGIOU, S., GLADYSZ, J. A., & MCCORMICK, F. B.

citation count

  • 30

complete list of authors

  • BUHRO, WE||ETTER, MC||GEORGIOU, S||GLADYSZ, JA||MCCORMICK, FB

publication date

  • June 1987