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C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands

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    C–H Bond Activation and Isoprene Polymerization by Rare-Earth-Metal Tetramethylaluminate Complexes Bearing Formamidinato N-Ancillary Ligands
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    † School of Chemistry, Monash University, 3800 Clayton, Victoria, Australia
    ‡ Institut für Anorganische Chemie, Universität Tübingen, Auf der Morgenstelle 18, D-72076 Tübingen, Germany
    § Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway
    ∥ School of Pharmacy & Molecular Sciences, James Cook University, Townsville, Queensland 4811, Australia
    *E-mail: [email protected] (G.B.D.); [email protected] (P.C.J.); [email protected] (R.A.).
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    Organometallics

    Cite this: Organometallics 2013, 32, 5, 1209–1223
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    https://doi.org/10.1021/om301010m
    Published January 9, 2013
    Copyright © 2013 American Chemical Society
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    Abstract

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    The bimetallic formamidinate complexes Ln(Form)(AlMe4)2 (Ln = Y, Form (ArNCHNAr) = EtForm (Ar = 2,6-Et2C6H3), MesForm (Ar = 2,4,6-Me3C6H2), DippForm (Ar = 2,6-iPr2C6H3), tBuForm (Ar = 2-tBuC6H4); Ln = La, Form = DippForm, tBuForm) were obtained in high yield by protonolysis reactions between formamidines (FormH) and homolepticrare-earth-metal tetramethylaluminates Ln(AlMe4)3. Y(Form)(AlMe4)2 (Form = EtForm, DippForm) were also prepared by treatment of Y(Form)[N(SiHMe2)2]2(thf) with trimethylaluminum after the former were prepared by the protonolysis of Y[N(SiHMe2)2]3(thf)2 complexes with EtFormH or DippFormH. The monomeric six-coordinate complexes Ln(Form)(AlMe4)2 (Ln = Y, Form = EtForm, MesForm, DippForm, tBuForm; Ln = La, Form = DippForm, tBuForm) show similar molecular structures with distorted-octahedral geometry and bidentate (N,N′) Form and AlMe4 ligands. The complex [La(EtFormAlMe3)(AlMe4)2](C7H8)1.5 from a protonolysis reaction between La(AlMe4)3 and EtFormH has the EtForm ligand adopting a configuration in which one nitrogen and one aryl substituent are coordinated to the eight-coordinate lanthanum center in an η1(N):η6(arene) manner. From the reaction of La(AlMe4)3 with MesFormH, C–H bond activation of an o-methyl group of the mesityl moiety occurred, yielding [La{η1(N):η6(Ar)-Me2CH2FormAlMe3}(AlMe3)(AlMe4)][La(Me2CH2FormAlMe3)(AlMe3)(AlMe4)](C6H14)1.5 (Me2CH2Form = MesForm-H(o-Me)), in which two linkage isomers of Me2CH2Form were observed. Investigations were carried out on the compounds [Ln(Form)(AlMe4)2] (Ln = Y, La; Form = EtForm, DippForm) as precatalysts activated by [Ph3C][B(C6F5)4] or [PhNMe2H][B(C6F5)4] in isoprene polymerization. While the lanthanum complexes showed narrower molecular weight distributions (PDI < 1.2), a stereodirecting role was evidenced for the cocatalysts (trityl borate, maximum 87% trans-1,4-selectivity; anilinium borate, maximum 82% cis-1,4-selectivity).

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    CIF files giving full crystallographic data for complexes 1a,b, 2a,b, 3bc, 3a, 4a,b, and 5a,b and a table giving selected bond angles of 2a,b, 3a, 4a,b, and 5a,b. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data have also been deposited at the Cambridge Crystallographic Data Centre under CCDC reference numbers 907682–907691 and can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.

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    Organometallics

    Cite this: Organometallics 2013, 32, 5, 1209–1223
    Click to copy citationCitation copied!
    https://doi.org/10.1021/om301010m
    Published January 9, 2013
    Copyright © 2013 American Chemical Society
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