By M. Davidson, A.K. Hughes, T.B. Marder, K. Wade
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Unlike the Cp" and C,Me, analogues"*" they are able to form ether adducts. As the structure of CpZr(C,F,) (CH,C(Me)CH,CHB(C,F,),) (OEG) (12) shows (Fig. 483(3) A, and indicates partial B-C double bond character; this might explain the apparently acidity of boryldiene ligands. aPF :ently low Lewis acidity Fig. 5 Molecular structure of 12. F Attempts to generate borole complexes fiom boryldiene precursors with sterically undemanding Cp ligands under a variety of conditions proved unsuccesshl, and only mixtures of decomposition products were obtained.
Species 7 is not stable in solution and undergoes disproportionation to generate compound 3b and ZrC4. The stability was improved by the introduction of a SiMe2 bridge to replace the isopropyl unit. The molecular structure of 8 is shown in Figure 8 and clearly shows the CGC nature. RlI I 2n-BuL1 2. ZIClJ = Zr;iR = H: X = C 7 % 8: M = T i . R = M e . X = S I Scheme 5 Figure 8 Moleciilar structure of 8 Applications to Polyolefin Catalysis 27 6 CONCLUSIONS The versatile complexation behavior of new ansa-type cyclopentadienyl o-carboranyl ligands HCpCMe2CBloHloCH, HCpCMe2CB1oHloCMe and HCsMe4SiMe2CB1oHloCH has been demonstrated, resulting in the synthesis of new classes of group 4 metallocene complexes including novel chiral bis(carborany1)group 4 complexes.
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