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A series of group 4 metallocenes possessing chiral ligand environments have been characterized and their structures are compared with their propylene polymerizations. Isotactic, syndiotactic, hemiisotactic, and atactic polypropylenes are produced selectively with chiral monoalkyl metallocene cations paired with perfluorotetraphenyl borate; analogous to the results obtained using methylaluminoxane as a cocatalyst. The relative catalyst stereospecificities suggest specific π‐face selectivities and nonbonded contacts. Trends with solvents, temperatures, and catalyst structures are consistent with contact ion pairing for iPr[CpFlu]Zr‐P(+) in liquid propylene. The specificities of differently structured metallocenes imply chain‐migratory monomer addition reactions.

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Two gadolinium(III) chelates, GdNP-DO3A (1-methlyene-(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triAcetate) and GdNP-DO3AM (1-methlyene(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triacetAMide), containing a single nitrophenolic pendant arm plus either three acetate or three amide pendant arms were synthesized and characterized. The properties of the gadolinium, terbium, and dysprosium complexes of these ligands were examined as a function of pH. The extent and mechanism of the changes in water relaxivity with pH of each gadolinium complex was found to differ substantially for the two complexes. The water relaxivity of Gd(NP-DO3A) increases from 4.1 mM(-1) s(-1) at pH 9 to 7.0 mM(-1) s(-1) at pH 5 as a result of acid-catalyzed dissociation of the nitrophenol from the lanthanide. The nitrophenol group in Gd(NP-DO3AM) does not dissociate from the metal center even at pH 5; therefore, the very modest increase in relaxivity in this complex must be ascribed to an increase in prototropic exchange rate of the bound water and/or phenolic protons.

Supplementary Material Available: Tables of atomic coordinates and thermal parameters, anisotropic thermal parameters, and bond distances and bond angles and figures showing ortep views of Re(0-2,6-C6H3-/-Pr2)4 (1) (6 pages). Ordering information is given on any current masthead page.

tion is supported by the 3 1 P NMR spectrum: The 6 values agree with that for the diphosphaallene 5 , n = 1 (6= 141.6), and an upfield shift on going from the E isomer to the Z isomer was also found, for example, in the case of bis(2,4,6-tri-rerf-butylphenyl)diphosphene ( E isomer, 6= 492; Z isomer, 6=368).'14'