Role of metals in borane clusters

Grimes, Russell N.

doi:10.1021/ar00085a004

Cited by 50 publications

(24 citation statements)

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“…Most of the early work on metallacarboranes by Hawthorne and co-workers used 12-vertex icosahedral systems although they also synthesized some metallacarboranes based on 10-vertex deltahedra. The early work on metallaboranes based on deltahedra with fewer than 10 vertices largely came from the laboratory of Grimes and coworkers [11].The development of the chemistry of hydrogen-rich metallaboranes based on nido polyhedra is much more recent and comes * Corresponding authors. …”

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confidence: 99%

The Wade–Mingos rules in seven-vertex dimetallaborane chemistry: Hydrogen-rich Cp2M2B5H9 systems of the second and third row transition metals

Brânzanic

Lupan

King

2015

Journal of Organometallic Chemistry

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confidence: 99%

The Wade–Mingos rules in seven-vertex dimetallaborane chemistry: Hydrogen-rich Cp2M2B5H9 systems of the second and third row transition metals

Brânzanic

Lupan

King

2015

Journal of Organometallic Chemistry

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“…Shortly thereafter, Grimes and co-workers 5 showed that similar metallaboranes could be synthesized based on smaller polyhedra using pentaborane-9, B 5 H 9 , as the boron hydride starting material. The initially discovered metallaboranes and dimetallaboranes had structures based on the most spherical so-called closo deltahedra with skeletal electron counts corresponding to the Wade-Mingos rules.…”

Section: Introductionmentioning

confidence: 99%

Dimetallaborane analogues of pentaborane

2015

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The structures of five-vertex dimetallaboranes Cp2M2B3H7 (Cp = η(5)-C5H5) of the second and third row transition metals, including the experimentally known Cp*2Rh2B3H7 (Cp* = η(5)-Me5C5), have been investigated by density functional theory. The predicted low-energy structures for Cp2M2B3H7 (M = Rh, Ir) are tetragonal pyramids similar to Cp*2Rh2B3H7 and pentaborane-9 B5H9 and consistent with their 14 Wadean skeletal electrons. Two Cp*2Rh2B3H7 structures with the same central Rh2B3 tetragonal prism are found with energies within ∼1 kcal mol(-1) of each other, consistent with the experimental observation of two isomers in solution. The electron-richer Cp2M2B3H7 (M = Pd, Pt) systems having 16 Wadean skeletal electrons are predicted to exhibit more open structures analogous to the known structure for the valence isoelectronic pentaborane-11 B5H11. Trigonal bipyramids with the metal atoms at equatorial vertices are typically found to be low-energy structures for the hypoelectronic Cp2M2B3H7 systems (M = Ru, Os, Re, Mo, W, Ta). In addition, the low-energy Cp2Re2B3H7 structures of the rhenium derivatives Cp2Re2B3H7 provide examples of structures based on a central Re2B2 tetrahedron with the Re-Re edge bridged by the third boron atom. Such structures can be derived from a trigonal bipyramid by the rupture of one of the axial-equatorial edges.

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“…Subsequent work by Grimes and co-workers [5] used pentaborane as a starting material to synthesize a variety of metallaboranes and metallacarboranes based on smaller polyhedra. Substitution of two CH vertices for BH vertices in a borane polyhedron provided neutral dicarbaboranes C 2 B ne2 H n (n ¼ 6e12) isoelectronic with the very stable polyhedral borane dianions B n H 2À n .…”

Section: Introductionmentioning

confidence: 99%