Bonding and electronic structure of Cp*2Ru2(B8H14), a metallaborane analogue of dinuclear pentalene complexes

Boucher, Benoît; Ghosh, Sundargopal; Halet, Jean‐François; Kahlal, Samia; Saillard, Jean‐Yves

doi:10.1016/j.jorganchem.2012.08.033

Cited by 11 publications

(4 citation statements)

References 23 publications

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“…Up to date the QTAIM study has been carried out of some polyhedral boranes, − ,,− and complexes containing M-(η 5 -C 2 B 3 ) bonding: [NMe4][3,3′-Co(1,2-C 2 B 9 H 11 ) 2 ], [3-(η 5 -C 5 Me 5 )-1,2-(PhCH 2 ) 2 - closo -3,1,2-RhC 2 B 9 H 9 ] and [3-{(1–3-η 3 )-C 8 H 13 }-1,2-(4′-MeC 6 H 4 ) 2 - pseudocloso -3,1,2-RhC 2 B 9 H 9 ] . A number of DFT calculations were published for comparative analysis of stable isomers for compounds containing M-B bonding, for example, [1,1,1-(PMe 3 ) 2 H-IrB 8 H 7 -8-Cl], Cp* 2 Ru 2 (B 8 H 14 ), isomers of 4-(η-C 10 H 8 )- 4 ,1, n - closo -MC 2 B 10 H 12 ( n = 6, 8, 10, 12; M = Ru, Fe), [(H) 2 Cl(PMe 3 ) 2 M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe 2 , Ph) . Regions of high value of ELF have the form of the dual polyhedron of the boron cage. , Besides, the QTAIM and ELI-D were applied to investigate bonding in isolated boron clasters, and crystalline MB 6 (M = Na, K, Rb, Ca, Sr, Ba, Sc, Y, La) and (NH 4 ) 2 (B 6 H 6 ) .…”

Section: Introductionmentioning

confidence: 99%

“…Up to date the QTAIM study has been carried out of some polyhedral boranes, 3−7,9,29−32 and complexes containing M-(η 5 34 A number of DFT calculations were published for comparative analysis of stable isomers for compounds containing M-B bonding, for example, [1,1,1-(PMe 3 ) 2 H-IrB 8 H 7 -8-Cl], 35 Cp* 2 Ru 2 (B 8 H 14 ), 36 39 Regions of high value of ELF have the form of the dual polyhedron of the boron cage. 40,41 Besides, the QTAIM and ELI-D were applied to investigate bonding in isolated boron clasters, 42 and crystalline MB 6 (M = Na, K, Rb, Ca, Sr, Ba, Sc, Y, La) 43 and (NH 4 ) 2 (B 6 H 6 ).…”

Section: Introductionmentioning

confidence: 99%

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Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]

et al. 2013

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Interaction of [Cu2B10H10] with 2,2'-bipyridine (bipy) afforded a novel binuclear discrete complex of the [Cu2(bipy)2B10H10] composition. Two copper(I) atoms coordinate a bridge boron cage through an apical edge and a triangular BBB face situated at its opposite apical vertices to form four 3c2e (CuHB) and one 2c2e Cu-B bonds. The charge density model was obtained by density functional theory calculations of isolated molecule and crystal. The resultant densities were analyzed using the quantum theory of atoms in molecules (QTAIM) and electron localizability indicator (ELI-D). The geometry and the topological parameters of copper(I) coordination environment were found to be sensitive to crystal-field effect. An annulus of flat electron density ρ(r) and small ∇(2)ρ(r) is formed at dianion faces. As a result, some of the expected B-B, Cu-B, or Cu-H bond critical points are absent. The topological instability in the region of multicentered bonds is observed. The Cu-B bonding was found to be presumably electrostatic in nature, which could be the reason of topological isomerism for copper(I) decaborates. The results show that an unambiguous real-space criterion for multicentered bonding between transition metals and polyhedral boron anions is not yet given. The molecular graph for this class of compounds does not provide a definitive picture of the chemical boding and can be complemented with other descriptors, such as virial graphs and the ELI-D distribution.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]

et al. 2013

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“…The lowest energy structures were then reoptimized at a higher level, that is, M06L/6‐311G(d,p)/SDD and these are the structures presented in the manuscript . This computational approach has proven to be reliable and gives results correlating well with available experimental data …”

Section: Theoretical Methodsmentioning

confidence: 57%

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

Lupan

King

2015

J Comput Chem

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Density functional theory shows that the lowest energy CpMoC3B(n-4)H(n-1) (n = 8, 9, 10, 11) structures are based on isocloso or similar deltahedra with the molybdenum atom at a degree 6 vertex. Such deltahedra include the capped pentagonal bipyramid for the 8-vertex system. Among such geometries the lowest energy structures have the carbon atoms at the lowest degree vertices (typically degree 4 vertices), no pairs of adjacent carbon atoms (i.e., no C-C edges), and the maximum number of Mo-C edges. Optimizing these factors favoring low-energy CpMoC3B(n-4)H(n-1) (n = 8, 9, 10, 11) structures leads to a unique lowest energy structure lying more than 10 kcal/mol below the next lowest energy structure for the 8-, 10-, and 11-vertex systems. However, the 9-vertex CpMoC3B5H8 system has three structures within 8 kcal/mol including a structure based on the closo tricapped trigonal prism rather than the isocloso 9-vertex deltahedron.

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“…However, owing to the high cost of osmium and the limited available information on osmaboranes, the predictions from this theoretical study would be more likely realized experimentally using analogous Cp 2 Ru 2 B nÀ2 H nÀ2 derivatives of the corresponding second row transition metal, namely ruthenium. In this connection, ruthenaboranes such as the 8-vertex species 23 Cp* 2 Ru 2 B 6 H 12 , the 10-vertex species [23][24][25] This paper reports our density functional theory studies on both the ruthenium and osmium derivatives Cp 2 M 2 B nÀ2 H nÀ2 (n = 8 to 12; M = Ru, Os). For each value of n two or three optimized structures lie substantially in energy below the other isomeric structures.…”

Section: Introductionmentioning

confidence: 99%

Hypoelectronic diruthenaboranes and diosmaboranes having eight to twelve vertices: capped isocloso and bicapped closo structures

Lupan

King

2013

New J. Chem.

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The oblate deltahedral structures for the experimentally known 2n À 4 Wadean skeletal electron systems Cp 2 Re 2 B nÀ2 H nÀ2 (Cp = Z 5 -R 5 C 5 ligand; R = H, CH 3 ; n = 8 to 12) differ radically from the more nearly spherical 2n skeletal electron isocloso deltahedra such as the known Cp 2 Fe 2 C 2 B nÀ4 H nÀ2 and 2n + 2 skeletal electron closo systems such as the extensive series of known Cp 2 Co 2 C 2 B nÀ4 H nÀ2 derivatives.Density functional theory has now been used to investigate the intermediate ''missing'' systems, namely the 2n À 2 Wadean skeletal electron systems Cp 2 M 2 B nÀ2 H nÀ2 (M = Ru, Os). The lowest energy such structures are predicted to have central deltahedra with n À 1 or n À 2 vertices capped by the remaining BH vertices. This generates larger deltahedra having one or two degree 3 vertices leading to tetrahedral cavities. In all of the lowest energy Cp 2 M 2 B nÀ2 H nÀ2 structures the metal atoms are located at the highest degree vertices, most frequently degree 6 vertices. These metal vertices share a deltahedral edge with M-M distances ranging from 2.7 to 2.9 Å and Wiberg bond indices of B0.3 to B0.4. The structural pattern changes drastically for the 12-vertex systems Cp 2 M 2 B 10 H 10 (M = Ru, Os) where the lowest energy structures are ''isoisocloso'' deltahedra having two adjacent degree 6 vertices for the metal atoms as well as eight degree 5 and two degree 4 vertices. Higher energy Cp 2 M 2 B 10 H 10 structures are based on a regular icosahedron with all degree 5 vertices having unusually short MRM edges of B2.2 to B2.3 Å with corresponding high Wiberg bond indices of B1.3 to B1.5 suggesting formal metal-metal triple bonds.

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Bonding and electronic structure of Cp*2Ru2(B8H14), a metallaborane analogue of dinuclear pentalene complexes

Cited by 11 publications

References 23 publications

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

Hypoelectronic diruthenaboranes and diosmaboranes having eight to twelve vertices: capped isocloso and bicapped closo structures

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Bonding and electronic structure of Cp*2Ru2(B8H14), a metallaborane analogue of dinuclear pentalene complexes

Cited by 11 publications

References 23 publications

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu2(bipy)2B10H10]

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu2(bipy)2B10H10]

Molybdatricarbaboranes as examples of isocloso metallaborane deltahedra with three carbon vertices

Hypoelectronic diruthenaboranes and diosmaboranes having eight to twelve vertices: capped isocloso and bicapped closo structures

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Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]

Theoretical QTAIM, ELI-D, and Hirshfeld Surface Analysis of the Cu–(H)B Interaction in [Cu₂(bipy)₂B₁₀H₁₀]