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Solid-state chlorine NMR of group IV transition metal organometallic complexes. 2009

Aaron J Rossini, and Ryan W Mills, and Graham A Briscoe, and Erin L Norton, and Stephen J Geier, and Ivan Hung, and Shaohui Zheng, and Jochen Autschbach, and Robert W Schurko
Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4.

Static solid-state (35)Cl (I = (3)/(2)) NMR spectra of the organometallic compounds Cp(2)TiCl(2), CpTiCl(3), Cp(2)ZrCl(2), Cp(2)HfCl(2), Cp*(2)ZrCl(2), CpZrCl(3), Cp*ZrCl(3), Cp(2)ZrMeCl, (Cp(2)ZrCl)(2)mu-O, and Cp(2)ZrHCl (Schwartz's reagent) have been acquired at 9.4 T with the quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) sequence in a piecewise manner. Spectra of several samples have also been acquired at 21.1 T. The electric field gradient (EFG) tensor parameters, the quadrupolar coupling constant (C(Q)) and quadrupolar asymmetry parameter (eta(Q)), are readily extracted from analytical simulations of the spectra. The (35)Cl EFG and chemical-shift tensor parameters are demonstrated to be sensitive probes of metallocene structure and allow for differentiation of monomeric and oligomeric structures. First-principles calculations of the (35)Cl EFG parameters successfully reproduce the experimental values and trends. The origin of the observed values of C(Q)((35)Cl) are further examined with natural localized molecular orbital (NLMO) analyses. The combination of experimental and theoretical methods applied to the model compounds are employed to structurally characterize Schwartz's reagent (Cp(2)ZrHCl), for which a crystal structure is unavailable. Aside from a few select examples of single-crystal NMR spectra, this is the first reported application of solid-state (35)Cl NMR spectroscopy to molecules with covalently bound chlorine atoms. It is anticipated that the methodology outlined herein will find application in the structural characterization of a wide variety of chlorine-containing transition-metal and main-group systems.

UI MeSH Term Description Entries
D008956 Models, Chemical Theoretical representations that simulate the behavior or activity of chemical processes or phenomena; includes the use of mathematical equations, computers, and other electronic equipment. Chemical Models,Chemical Model,Model, Chemical
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D009682 Magnetic Resonance Spectroscopy Spectroscopic method of measuring the magnetic moment of elementary particles such as atomic nuclei, protons or electrons. It is employed in clinical applications such as NMR Tomography (MAGNETIC RESONANCE IMAGING). In Vivo NMR Spectroscopy,MR Spectroscopy,Magnetic Resonance,NMR Spectroscopy,NMR Spectroscopy, In Vivo,Nuclear Magnetic Resonance,Spectroscopy, Magnetic Resonance,Spectroscopy, NMR,Spectroscopy, Nuclear Magnetic Resonance,Magnetic Resonance Spectroscopies,Magnetic Resonance, Nuclear,NMR Spectroscopies,Resonance Spectroscopy, Magnetic,Resonance, Magnetic,Resonance, Nuclear Magnetic,Spectroscopies, NMR,Spectroscopy, MR
D009942 Organometallic Compounds A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed) Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D002712 Chlorides Inorganic compounds derived from hydrochloric acid that contain the Cl- ion. Chloride,Chloride Ion Level,Ion Level, Chloride,Level, Chloride Ion
D018360 Crystallography, X-Ray The study of crystal structure using X-RAY DIFFRACTION techniques. (McGraw-Hill Dictionary of Scientific and Technical Terms, 4th ed) X-Ray Crystallography,Crystallography, X Ray,Crystallography, Xray,X Ray Crystallography,Xray Crystallography,Crystallographies, X Ray,X Ray Crystallographies
D028561 Transition Elements Elements with partially filled d orbitals. They constitute groups 3-12 of the periodic table of elements. Elements, Transition

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