Structural Studies of Coupling Products Formed Between (C6H5)CH=N(C6H5) and the M(C5H5)(6,6-dmch) Fragments (M = Ti, Zr; dmch = dimethylcyclohexadienyl)

The reactions of Ti(C5H5)(6,6-dmch)(PMe3) and Zr(C5H5)(6,6-dmch)(PMe3)2 with two equivalents of C6H5C(H)=N(C6H5) have led to couplings of the imines to the 1,5 (terminal) positions of the 6,6-dmch ligands. In both cases the PMe3 ligands are lost, and the metal complexes each attain 18 electron configurations via η5-(C5H5), η3-allyl, and bis(π-amide) coordination. The complexes each crystallize in the monoclinic space group P21/c. For the titanium complex, a = 10.4336(1) A, b = 9.0407(1) A, c = 32.5547(6) A, β = 94.2939(5)°, V = 3062.17(7) A3, Dcalc = 1.264 at 200(1) K. For the zirconium complex, a = 13.8900(3) A, b = 10.0873(2) A, c = 22.4543(6) A, β = 90.7638(7)°, V = 3145.85(12) A3, Dcalc = 1.322 at 150(1) K. The reactions of M(C5H5)(6,6-dmch) fragments (M = Ti, Zr; dmch = dimethylcyclohexadienyl) with two equivalents of (C6H5)(H)C=N(C6H5) have led to couplings at the dienyl termini, resulting in 18 electron π-allyl, bis(π-amide) complexes.