NDLI: Identification of non-classical C–H⋯M interactions in early and late transition metal complexes containing the $CH(ArO)

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Lein, Matthias Nielson, Alastair J. Harrison, John A.
Description	Author Affiliation: Lein M ( School of Chemical and Physical Sciences, Victoria University of Wellington, Kelburn Campus, Wellington 6140, New Zealand.)
Abstract	The fully optimised DFT structure of the $d^{0}$ complex $[\{CH(ArO)_{3}\}Ti(NEt_{2})]$ (2) at the B3LYP level compares well with the distorted tetrahedral geometry shown by the X-ray crystal structure. QTAIM analysis of the electron density associated with the C–H⋯Ti interaction shows a well defined bond critical point, a bond path between the hydrogen and titanium centres and a negative value for the energy density indicative of covalency. A natural bond orbital (NBO) picture of the interaction shows that the C–H σ bond electron density donates to a d hybrid orbital on the metal in a linear fashion. Calculated IR and NMR data for the components of the interaction are consistent with experiment. The computed structures for $[\{CH(ArO)_{3}\}Ti(OPh)]$ (3), $[\{CH(ArO)_{3}\}Zr(NEt_{2})]$ (4), $[\{CH(ArO)_{3}\}Hf(NEt_{2})]$ (5), show tetrahedral geometries and QTAIM and NBO properties similar to (2). $[\{CH(ArO)_{3}\}Mo(NEt_{2})]$ (6) shows distortion of the tripodal ligand and a reduced C–H⋯M bond angle with properties more consistent with a C–H⋯M side-on donor interaction. In $[\{CH(ArO)_{3}\}Fe(NEt_{2})]$ (7) the C–H⋯M bond angle is linear and involves a donor interaction. An energy minimised structure maintaining the three fold coordination to the tripodal ligand was not obtained for $[\{CH(ArO)_{3}\}Ni(NEt_{2})]^{2−}$ but changing from a diethyl amide ligand to phenolato gave energy minimised $[\{CH(ArO)_{3}\}Ni(OPh)]^{2−}$ (8). This structure shows a distorted square planar geometry with a substantially bent phenoxo ligand and a near linear C–H⋯M covalent interaction with donor and back bonding properties. The work shows that linear C–H⋯M interactions can have both agostic and weak hydrogen bond-like covalency.
ISSN	14779226
Issue Number	30
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-08-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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