First-row transition metal bis(amidinate) complexes; Planar four-coordination of Fe-II enforced by sterically demanding aryl substituents

The sterically hindered benzamidinate ligand [PhC(NAr)(2)](-) (Ar = 2,6-iPr(2)C(6)H(3)) has been employed to prepare bis(amidinate) complexes [{PhC(NAr)(2)}(2)M] of the divalent first-row transition metals Cr-Ni (1-5). For Cr (planar), Mn and Co (tetrahedral) the observed structures follow the electronic preference for the metal ion in its highest spin multiplicity, as determined by DFT calculations. Remarkably, the Fe derivative adopts a distorted planar structure while retaining the high-spin (S = 2) configuration. This rare combination due to reduced interligand steric interactions in the planar vs. the tetrahedral structure, combined with a relatively small electronic preference of Fen for the tetrahedral environment. Thus, the simple bidentate ligand N,N '-diarylbenzamidinate provides a convenient means to make this unusual species accessible for further study. (c) Wiley-VCH Verlag GmbH & Co

Accurate Prediction of Copolymerization Statistics in Molecular Olefin Polymerization Catalysis: The Role of Entropic, Electronic, and Steric Effects in Catalyst Comonomer Affinity

Accurate in silica prediction of copolymerization performance of olefin polymerization catalysts is demonstrated. It is shown by the example of 19 metallocene and post-metallocene group IV metal (Ti, Zr, Hf) systems that DFT (M06-2X(PCM)/TZ//TPSSTPSS/DZ) can accurately describe the copolymerization factor r(e): i.e., the competition of ethene and propene for insertion in metal n-alkyl bonds. Experimental r(e) values were computationally reproduced with a mean average deviation (MAD) and maximum deviation of only 0.2 and 0.5 kcal/mol, respectively. Both dispersion and solvent corrections play a crucial role in achieving this accuracy. Ethene insertion is found to be entropically favored for all catalysts due to a combination of symmetry factors and less congested insertion geometries. The enthalpic preference for either ethene or propene is catalyst dependent. The predictions are based on straightforward calculation of relevant insertion transition state energies; there are no indications for a shift in rate-limiting step from insertion to e.g. olefin capture or chain rotation

Naked (C5Me5)2M Cations (M = Sc, Ti, and V) and Their Fluoroarene Complexes

The ionic metallocene complexes [Cp*2M][BPh4] (Cp* = C5Me5) of the trivalent 3d metals Sc, Ti, and V were synthesized and structurally characterized. For M = Sc, the anion interacts weakly with the metal center through one of the phenyl groups, but for M = Ti and V, the cations are naked. They each contain one strongly distorted Cp* ligand, with one (V) or two (Ti) agostic C-H···M interactions involving the Cp*Me groups. For Sc and Ti, these Lewis acidic species react with fluorobenzene and 1,2-difluorobenzene to yield [Cp*2M(κF-FC6H5)n][BPh4] (M = Sc, n = 2; M = Ti, n = 1) and [Cp*2M(κ2F-1,2-F2C6H4)][BPh4], the first examples of κF-fluorobenzene and κ2F-1,2-difluorobenzene adducts of transition metals. With the perfluorinated anion [B(C6F5)4]-, both Sc and Ti form [Cp*2M(κ2F-C6F5)B(C6F5)3] contact ion pairs. The nature of the metal-fluoroarene interaction was studied by density functional theory (DFT) calculations and by comparison with the corresponding tetrahydrofuran (THF) adducts and was found to be predominantly electrostatic for all metals studied.