Emslie Group - Selected Research Highlights

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Research Highlights from our group are described below:

(1a) Electropositive Metal Complexes of Extremely Rigid Pincer Ligands: Thermally Robust Rare Earth and Actinide Complexes for Small Molecule Activation and Catalysis

- Synthesis of the first examples of non-cyclopentadienyl actinide alkyl cations; all are also rare examples of arene-coordinated metal alkyl cations (Organometallics, 2008, 15-17 & 2009, 1891-1899).

- The first example of double alkyl abstraction to form a dicationic actinide complex (Organometallics, 2008, 15-17).

- A detailed structural and computational (ADF and AIM) study of U–SAr2 versus U–OAr2 bonding (Dalton Trans. 2012, 8175-8189).

- Observation of unusual alkyl exchange reactivity in the chemistry of uranium (Organometallics, 2013, 32, 1466−1474).

- A thorium complex, [LTh(CH2SiMe3)2], with thermal stability comparable or greater than the Cp* analogue (Organometallics, 2006, 692-701).

- A unique 'Grignard adduct' in which a thorium dihalide is bound via Th-X-Mg linkages to an MeMgX (X = Cl or Br) unit (JOMC, 2010, 695, 2798-2803).

(1b) Electropositive Metal Complexes of Extremely Rigid Pincer Ligands: Metal-Alkane Complexes

- Isolation of the first complexes exhibiting main group element–alkane interactions, and characterization of the nature of these interactions by DFT (Angew Chem. Int. Ed. 2013, 52, 1696-1699).

(2) Group 13 Lewis Acid Appended Transition Metal Complexes: Studies of Metal-Ligand Bonding and Cooperative Catalysis.

- Rare examples of alkyl/aryl exchange between a transition metal and a pendant borane (Organometallics, 2015, 34, 2737).

- DBA displacement from palladium by FcPPB, a phosphine-phosphine-borane ambiphilic ligand, but not by FcPPP, the trisphosphine analogue (Organometallics, 2015, 34, 4093).

- Synthesis of a unique phosphine-thioether-borane ligand, and use of this ligand to isolate the first h2BC- and h3BCC-coordinated arylborane complexes (Organometallics 2006, 2412 & 5035, Organometallics 2008, 5317, and Inorg. Chem. 2010, 4060). This, and our recently synthesized FcPPB ligand are the only ambiphilic ligands with a strongly Lewis acidic borane positioned in the terminal position of a donor-donor-acceptor array.

- Isolation of the first 1-borataallyl complex, and the first complex displaying an alkyl/borataalkene coordination mode. In both cases the vinylborane is h3-coordinated to the metal via boron and the two sp2-hybrdized carbon atoms (Angew. Chem. Int. Ed. 2010, 2716),.

- Isolation of a complex in which an enone is bound between Pd and B; the enone is structurally activated to the extent that the complex is best described as an h3-boratoxyallyl zwitterion (Organometallics 2006, 2412).

- Isolation of rare (X = Cl) or unprecedented (X = Br or I) complexes containing M-X-BR3 linkages. The nature of Pt-Cl-B and Pt-I-B bonding in these complexes was studied in detail using DFT calculations (Inorg. Chem. 2010, 4060 and Dalton Trans. 2012, 3523).

- Isolation of zwitterionic
[Rh(CO)(TXPB-F)] in which fluoride has been abstracted from rhodium by the borane (Inorg. Chem. 2010, 4060).

- Isolation of bridging Rh–Fe borataaminocarbyne complexes formed by intramolecular isonitrile–borane coordination (Organometallics. 2013).

- Synthesis of a borane-appended analogue of the dppf ligand, FcPPB (Chem. Eur. J.,2014, 20, 16899).

- First examples of reversible conversion between h3BCC- and h2BC- and h1B-arylborane coordination modes (Chem. Eur. J., 2014, 20, 16899).

- In-situ synthesis of the first vinylborane-appended ambiphilic ligand (Chem. Eur. J.,2014, 20, 16899).

- The first direct comparison between h3BCC-coordinated arylborane and vinylborane complexes (Chem. Eur. J., 2014, 20, asap: 10.1002/chem.201404846).

(3) New Organomeallic Precursors and Reactivity for Metal ALD (Atomic Layer Deposition).

- Solution deposition of manganese metal via the reactions of [{Mn(CH2CMe3)2}4] and [{Mn(CH2EMe3)2}x(Me2P(CH2)xPMe2)x] (E = C or Si; x = 1 or 2) complexes with H2 (Organometallics, 2016, asap).

- Synthesis of volatile and thermally robust mixed alkyl / allyl complexes of manganese. As an example, [(h3-allylTMS2)Mn{C(SiMe3)3}(PMe3)] {allylTMS2 = 1,3-C3H3(SiMe3)2} is a bright-red pyrophoric solid that sublimes at 70 °C (10 mTorr) and is unchanged after 24h in a sealed flask at 100 °C (Organometallics, 2014, 33, 1467).

- Use of ZnEt2 and AlMe3 as co-reactants for pulsed-CVD of copper metal films (Chem. Mater., 2010, 4844-4853).

- Elucidation of the reaction pathways responsible for copper deposition in the solution reactions of CuL2 (L = N-isopropylpyrrolylaldimine) with ZnEt2, AlMe3 and BEt3 (Chem. Mater., 2010, 4854-4866).