Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH2CMe2CH2CH═CH2)2]−

Liu, Sumeng; Smith, Brett A.; Kirkland, Justin K.; Vogiatzis, Konstantinos D.; Girolami, Gregory S.

doi:10.1021/acs.inorgchem.1c00737

Cited by 2 publications

(2 citation statements)

References 97 publications

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“…To provide additional insights into the ligand-field properties of the BDAM ligand, extended-transition-state natural orbitals for chemical valence (ETS-NOCV) analyses were performed on Co(BDAM) 3 , 4 . ETS-NOCV calculations have been extensively applied to elucidate metal–ligand bonding; of relevance here is the use of this method to investigate agostic C–H–M – and covalent B–H–M interactions. ,– …”

Section: Resultsmentioning

confidence: 99%

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Lastowski,

Yarranton,

Zhu

et al. 2023

J. Am. Chem. Soc.

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We describe new compounds of stoichiometry M(CH2NMe2BH3)3 (M = Ti, Cr, and Co), each of which contains three chelating boranatodimethylaminomethyl (BDAM) ligands. In all three compounds, the BDAM anion, which is isoelectronic and isostructural with the neopentyl group, is bound to the metal center at one end by a metal–carbon σ bond and at the other by one three-center M–H–B interaction. The crystal structures show that the d1 titanium(III) compound is trigonal prismatic (or eight-coordinate, if two longer-ranged M···H interactions with the BH3 groups are included), whereas the d3 chromium(III) compound and the d6 cobalt(III) compounds are both fac-octahedral. The Cr and Co compounds exhibit two rapid dynamic processes in solution: exchange between the Δ and Λ enantiomers and exchange of the terminal and bridging hydrogen atoms on boron. For the Co complex, the barrier for Δ/Λ exchange (ΔG ⧧ 298 = 10.1 kcal mol–1) is significantly smaller than those seen in other octahedral cobalt(III) compounds; DFT calculations suggest that Bailar twist and dissociative pathways for Δ/Λ exchange are both possible mechanisms. The UV–vis absorption spectra of the cobalt(III) and chromium(III) species show that the ligand field splittings Δo caused by the M–H–B interactions are unexpectedly large, thus placing them high on the spectrochemical series (near ammonia and alkyl groups); their nephelauxetic effect is also large. The DFT calculations suggest that these properties of M–H–B interactions are in part a consequence of their three-center nature, which delocalizes electron density away from the metal center and reduces electron–electron repulsions.

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Section: Resultsmentioning

confidence: 99%

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Lastowski,

Yarranton,

Zhu

et al. 2023

J. Am. Chem. Soc.

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“…Yield: 0. 90 Single crystals, grown from either diethyl ether (1 and 3) or tetrahydrofuran (2), were mounted on glass fibers with Paratone oil (Exxon) and immediately cooled to −80 °C in a cold stream of nitrogen gas on the diffractometer. Standard peak search and indexing procedures, followed by least-squares refinement, yielded the cell dimensions given in Table 4.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Synthesis and Characterization of Ether Adducts of Thorium Tetrahydroborate Th(BH₄)₄ and Chemical Vapor Deposition of Thorium Boride Thin Films

et al. 2023

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Treating ThCl4 with LiBH4 in various ethereal solvents affords the adducts Th(BH4)4(Et2O)2, Th(BH4)4(thf)2, and Th(BH4)4(dme) (thf = tetrahydrofuran and dme = 1,2-dimethoxyethane). The structures of these three compounds have been established by single-crystal X-ray diffraction: if the tetrahydroborate groups are considered as occupying one coordination site, the Et2O and thf complexes adopt trans-octahedral coordination geometries, whereas the dme complex exhibits a cis-octahedral structure. All four BH4 – ligands in each compound are tridentate, rendering each thorium center 14-coordinate. The Th···B distances range from 2.64 to 2.67 Å, and the Th–O bond lengths are 2.47–2.52 Å. We propose that crystals of Th(BH4)4(thf)2 are isomorphous with those of U(BH4)4(thf)2, but owing to pseudosymmetry the latter was reported in a unit cell that was too small by a factor of 2. IR spectra and 1H and 11B NMR data are reported as well. All three adducts are volatile, subliming readily at 60 °C and 10–4 Torr, making them potentially useful as precursors for the chemical vapor deposition (CVD) of thin films of thorium boride. Passage of Th(BH4)4(Et2O)2 over glass, Si(100), and aluminum substrates heated to 350 °C yields amorphous films of approximate stoichiometry ThB2; films deposited from Th(BH4)4(thf)2 have stoichiometries closer to ThB2.5 and contain some oxygen. Auger, XPS, XRD, and SEM studies of these films are reported.

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Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH₂CMe₂CH₂CH═CH₂)₂]⁻

Cited by 2 publications

References 97 publications

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Synthesis and Characterization of Ether Adducts of Thorium Tetrahydroborate Th(BH₄)₄ and Chemical Vapor Deposition of Thorium Boride Thin Films

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Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH2CMe2CH2CH═CH2)2]−

Cited by 2 publications

References 97 publications

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH2NMe2BH3)3 Complexes of Titanium, Chromium, and Cobalt

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH2NMe2BH3)3 Complexes of Titanium, Chromium, and Cobalt

Synthesis and Characterization of Ether Adducts of Thorium Tetrahydroborate Th(BH4)4 and Chemical Vapor Deposition of Thorium Boride Thin Films

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Nature of the Short Rh–Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH₂CMe₂CH₂CH═CH₂)₂]⁻

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Three-Center M–H–B Bonds Are Strong Field Interactions. Synthesis and Characterization of M(CH₂NMe₂BH₃)₃ Complexes of Titanium, Chromium, and Cobalt

Synthesis and Characterization of Ether Adducts of Thorium Tetrahydroborate Th(BH₄)₄ and Chemical Vapor Deposition of Thorium Boride Thin Films