Pi -Allyl to Sigma -Allyl Photochemical Rearrangements as Precursors to C-H Activation.

Thomas E. Bitterwolf, Abdel A. Saygh, J. Timothy Bays

Department of Chemistry, University of Idaho, Moscow, ID, 2 Department of Chemistry

Joyce E. Shade

U. S. Naval Academy, Annapolis, MD

Arnold L. Rheingold, Glenn Yap, Louise M. Lable-Sands

Department of Chemistry, University of Delaware, Newark, DE.

Photolysis of [Mo(CO)₂(h ³-CH_{5)]2(h ⁵, h⁵-C5H4-CMe2-C5H4) in benzene under an atmosphere of CO yields the "twist" derivative [Mo(CO)3][Mo(CO)2( h³-C3H5)](h ⁵, h ⁵:h ¹-C5H4-CMe2-C5H3), I, while photolysis of Mo(CO)2(h³-C3H5)(h⁵-C5H4-CH2-C6H5) gives [Mo(CO)3]( h⁵, h ¹-C5H4-CH2-C6H4), II. In both cases a vacant site on the metal is created by a pi -allyl to sigma -allyl photochemical rearrangement.}