Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(iii) and Hf(iii)

Grant, Lauren N.; Miehlich, Matthias E.; Meyer, Karsten; Mindiola, Daniel J.

doi:10.1039/c7cc08815a

Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(iii) and Hf(iii)

Journal Article · Fri Jan 26 04:00:00 EST 2018 · ChemComm

DOI:https://doi.org/10.1039/c7cc08815a· OSTI ID:1843641

^[1]; Miehlich, Matthias E. ^[2]; ^[2]; ^[3]

Univ. of Pennsylvania, Philadelphia, PA (United States); Program Manager, Catalysis Science Office of Basic Energy Sciences U.S. Department of Energy
Friedrich-Alexander Univ. Erlangen-Nürnberg (FAU) (Germany)
Univ. of Pennsylvania, Philadelphia, PA (United States)

Reduction of the group 4 transition metal precursors [(PN)₂MCl₂] (M = Zr (1), and Hf (2)); PN– = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide), both readily prepared by transmetallation of 2 LiPN with [MCl₄(THF)₂], with a slight excess of KC₈, resulted in the isolation of the trivalent complexes [(PN)₂MCl] (M = Zr (3), and Hf (4)). Complexes 1–4 were all identified by solid-state X-ray diffraction analysis, whereas in the case of 3 and 4 low temperature X-band EPR spectroscopy allowed for the identification of these metal-centered d¹ radicals. Here, a comparison with the isostructural and isoelectronic but more stable [(PN)₂TiCl] is also presented.

Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: SC0012486

OSTI ID:: 1843641

Journal Information:: ChemComm, Journal Name: ChemComm Journal Issue: 16 Vol. 54; ISSN 1359-7345

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

References (17)

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors Fryzuk, Michael D.; Jafarpour, Laleh; Rettig, Steven J. Organometallics, Vol. 18, Issue 20 https://doi.org/10.1021/om990096+	journal	August 1999
Characterization and interconversion of metal-phosphorus single and double bonds: bis(cyclopentadienyl)zirconium and -hafnium bis(diorganophosphide) complexes Baker, R. T.; Whitney, J. F.; Wreford, S. S. Organometallics, Vol. 2, Issue 8 https://doi.org/10.1021/om50002a022	journal	August 1983
Synthesis, Structure, and Reactions of (.eta.5-C5H5)3Zr Lukens, Wayne W.; Andersen, Richard A. Organometallics, Vol. 14, Issue 7 https://doi.org/10.1021/om00007a050	journal	July 1995
Synthesis, Characterization, and Catalytic Activities for the Polymerization of Olefins Promoted by Zirconium(III) and Titanium(III) Allyl Complexes Ray, Biswajit; Neyroud, Tali Gueta; Kapon, Moshe Organometallics, Vol. 20, Issue 14 https://doi.org/10.1021/om0009942	journal	July 2001
Structural elucidation of a mononuclear titanium methylidene Grant, Lauren N.; Ahn, Seihwan; Manor, Brian C. Chemical Communications, Vol. 53, Issue 24 https://doi.org/10.1039/C7CC00654C	journal	January 2017
Catalytic Hydrosilylation of the Carbonyl Functionality via a Transient Nickel Hydride Complex Tran, Ba L.; Pink, Maren; Mindiola, Daniel J. Organometallics, Vol. 28, Issue 7 https://doi.org/10.1021/om801160j	journal	April 2009
Mononuclear and Terminally Bound Titanium Nitrides Carroll, Maria E.; Pinter, Balazs; Carroll, Patrick J. Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04853	journal	July 2015
Zr and Hf metallocenes. Study of the structure of a novel mononuclear zirconium trivalent organometallic Urazowski, I. F.; Ponomaryev, V. I.; Nifant'ev, I. E. Journal of Organometallic Chemistry, Vol. 368, Issue 3 https://doi.org/10.1016/0022-328X(89)85406-3	journal	June 1989
Molecular titanium nitrides: nucleophiles unleashed Grant, Lauren N.; Pinter, Balazs; Kurogi, Takashi Chemical Science, Vol. 8, Issue 2 https://doi.org/10.1039/C6SC03422E	journal	January 2017
Synthesis of mononuclear paramagnetic zirconium(III) derivatives Fryzuk, Michael D.; Mylvaganam, Murugesapillai; Zaworotko, Michael J. Journal of the American Chemical Society, Vol. 115, Issue 22 https://doi.org/10.1021/ja00075a062	journal	November 1993
Mixed-sandwich complexes of zirconium(III) and hafnium(III): Potential analogues of [U(η-C8H6{SiiPr3-1,4}2)(η-Cp∗)] for cyclooligomerisation of CO Button, Z. E.; Cloke, F. G. N.; Morley-Smith, N. A. Journal of Organometallic Chemistry, Vol. 695, Issue 25-26 https://doi.org/10.1016/j.jorganchem.2010.09.034	journal	December 2010
Absolute Metal−Ligand σ Bond Enthalpies in Group 4 Metallocenes. A Thermochemical, Structural, Photoelectron Spectroscopic, and ab Initio Quantum Chemical Investigation King, Wayne A.; Di Bella, Santo; Gulino, Antonino Journal of the American Chemical Society, Vol. 121, Issue 2 https://doi.org/10.1021/ja9822815	journal	January 1999
Synthesis, structure and reactivity of mononuclear paramagnetic complexes of zirconium and hafnium Fryzuk, Michael D.; Mylvaganam, Murugesapillai; Zawarotko, Michael J. Polyhedron, Vol. 15, Issue 4 https://doi.org/10.1016/0277-5387(95)00287-3	journal	February 1996
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Formation of Trivalent Zirconocene Complexes from ansa -Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study Lenton, Taylor N.; Bercaw, John E.; Panchenko, Valentina N. Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja403170u	journal	July 2013
Structure of (η5-C5Me5)(η8-C8H8)Zr, an aromatic mixed sandwich complex of zirconium(III) Rogers, Robin D.; Teuben, Jan H. Journal of Organometallic Chemistry, Vol. 359, Issue 1 https://doi.org/10.1016/0022-328X(89)85249-0	journal	January 1989
Facile Reduction of a Dialkyl Zirconium(IV) Octaethylporphyrin (OEP) Complex by H2: Crystal Structure and Spectroscopic Characterization of [(OEP)ZrCH2SiMe3] Brand, Holger; Arnold, John Angewandte Chemie International Edition in English, Vol. 33, Issue 1 https://doi.org/10.1002/anie.199400951	journal	January 1994

Similar Records

Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr( iii ) and Hf( iii )

Journal Article · Sun Dec 31 23:00:00 EST 2017 · ChemComm · OSTI ID:1539868

Molecular Zirconium Nitride Super Base from a Mononuclear Parent Imide

Journal Article · Sun Dec 02 23:00:00 EST 2018 · Journal of the American Chemical Society · OSTI ID:1843643

C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex

Journal Article · Fri Jul 27 00:00:00 EDT 2018 · Journal of the American Chemical Society · OSTI ID:1843644

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Arrested disproportionation in trivalent, mononuclear, and non-metallocene complexes of Zr(iii) and Hf(iii)

Citation Formats

References (17)

Linked Research (1)

Similar Records

Related Subjects