Rhodathiaborane reaction cycles driven by C2H4 and H2: synthesis and characterization of [(H)2(PPh3)RhSB8H7(PPh3)] and [(η2-C2H4)(PPh3)RhSB8H7(PPh3)]

Luaces, Susana; Macı́as, Ramón; Artigas, M.; Lahoz, Fernando J.; Oro, Luis A.

doi:10.1039/c4dt03677h

Cited by 4 publications

(3 citation statements)

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“…Thus, in compound 9, the metal hydride, having the choice, avoids lying trans to cage boron vertices. The same tendency has been identified in a significant number of hydridometallathiaboranes 9, 14,15,18 where the exo-polyhedral ligand orientation is mainly controlled by cage S atoms that, in the metal-thiaborane linkage, force the hydride ligands to occupy positions trans to the heteroatom: the strong transinfluence hydride ligand avoids the cage B atoms that exhibit a stronger structural trans effect than the cage sulfur atoms.…”

Section: X-ray Diffraction Analysissupporting

confidence: 55%

“…This reaction reveals an interesting structural redox switchability that combines the {RhH(PPh 3 ) 2 } group and the {SB 8 H 8 } polyhapto ligand in 1, which has yielded new stoichiometric and catalytic cycles driven by dihydrogen and ethylene. 15 Similar to the 11-vertex rhodathiaborane introduced above, this reactivity opens the door for a postsynthetic modification of the 10-vertex clusters by the systematic change of the exopolyhedral ligands bound to a boron vertex of the {SB 8 H 8 }-fragment. We hypothesized that varying the boron-ligated Lewis base could be a powerful way to tune the reactivity of the 10-vertex rhodathiaboranes.…”

Section: Introductionmentioning

confidence: 84%

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Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning

et al. 2016

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It has been demonstrated that the reaction of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] () with PPh3 affords the boron substituted rhodathiaborane-PPh3 adduct, [6,6-(PPh3)2-9-(PPh3)-arachno-6,5-RhSB8H9] (). Building upon this reaction, we report herein that the 10-vertex hydridorhodathiaborane reacts with the Lewis bases, PCy3, py, 2-Mepy, 2-Etpy, 3-Mepy and 4-Mepy to form the rhodathiaborane-ligand adducts, [6,6-(PPh3)2-9-(L)-arachno-6,5-RhSB8H9], where L = PCy3 (), 2-Mepy (), 2-Etpy (), py (), 3-Mepy () or 4-Mepy (), and [8,9-μ-(H)-9-(PPh3)2-8-(L)-arachno-9,6-RhSB8H8], where L = py (), 3-Mepy () or 4-Mepy (). The selectivity of the reactions depended on the nature of the entering Lewis bases, affording the 6,5-isomers, , , and as single products for PPh3, PCy3, 2-Mepy and 2-Etpy; and mixtures of the 6,5-/9,6-regioisomers, /, / and / for py, 3-Mepy and 4-Mepy, respectively. The molecular structures of both regioisomers were characterized by X-ray diffraction analysis for the 6,5-isomers, and , and for the 9,6-isomers, and . Variable temperature NMR studies of the reaction between and PPh3 or 2-Mepy demonstrated that at low temperatures there is formation of the 9,6-species that subsequently isomerizes to the 6,5-regioisomer, indicating that for the more sterically hindered Lewis bases, PPh3, 2-Mepy and PCy3, the latter isomer is more stable and accessible through an intramolecular {Rh(PPh3)2} vertex flip. The formation of both isomers with py, 3-Mepy and 4-Mepy indicates that the kinetic and thermodynamic energies of the 6,5 and 9,6 rhodathiaborane-ligand adducts are similar for these Lewis bases. Lewis base bonding to exo-polyhedral boron vertices results in a change of the metal coordination from pseudo-octahedral Rh(iii) in to pseudo-square planar Rh(i) in the adducts. The chemistry described here highlights the remarkable structural flexibility of these polyhedral boron-containing compounds, their modular architecture and their easy postsynthetic modification.

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Section: X-ray Diffraction Analysissupporting

confidence: 55%

Section: Introductionmentioning

confidence: 84%

Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning

et al. 2016

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“…Earlier reports on the reactivity of unsaturated [(Cp*Cr) 2 B 4 H 8 ] with CS 2 demonstrate the hydroboration of CS 2 to the methanedithiolato ligand . In general, the insertion or coordination of a heteroatom to the polyhedral borane imparts an electronic effect that ultimately modifies the reactivity of the parent compound . As a result, we have performed the reactivity of [(Cp*M) 2 (B 2 H 6 ) 2 ] (M = Mo and W) with CS 2 and report the synthesis and comprehensive electronic structures of some new bimetallic dithiolato complexes of the group 6 metals.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

et al. 2017

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The quadruply bridged bimetallic dithiolato complex [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] (3) and the open-cage triple-decker complex [(Cp*W) 2 (μ-S)(μ-η 4 :η 4 -B 2 H 2 S 2 )] (2) have been prepared by treatment of CS 2 with in situ generated [(Cp*W) 2 (B 2 H 6 ) 2 ] (1) obtained by the reaction of [Cp*WCl 4 ] with [LiBH 4 ·thf ]. The solid-state X-ray diffraction structures of these complexes show the presence of doubly bridging η 2 -S 2 B 2 H 2 and η 2 -S 2 CH 2 ligands with a short W-W bond. While many dimolybdenumsulfur compounds are known, examples of the tungstendithilato complexes are relatively few, and in this respect, the isolation of [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] represents a rare exam- [a] 5434 ple of this type. Electronic-structure analysis, on the grounds of density functional theory (DFT), together with X-ray diffraction studies, has rationalized the presence of short W-W and B-B bonds. Large HOMO-LUMO gaps have been observed for both compounds, which is consistent with their thermodynamic stability. All of the compounds have been characterized by mass spectrometry, IR spectroscopy, and 1 H NMR, 11 B NMR, and 13 C NMR spectroscopy in solution, and the structural architectures have been unambiguously established by X-ray diffraction crystallographic analysis. Scheme 1. Structurally characterized dithiolato-bridged binuclear transitionmetal complexes [Mo = CpMo (I-V) and V = CpV (VI)]. [11a,13] Scheme 2. Synthesis of compounds 2, 2a, and 3.

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Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

et al. 2017

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Rhodathiaborane reaction cycles driven by C₂H₄ and H₂: synthesis and characterization of [(H)₂(PPh₃)RhSB₈H₇(PPh₃)] and [(η²-C₂H₄)(PPh₃)RhSB₈H₇(PPh₃)]

Abstract: New 10-vertex rhodathiaboranes are reported to exhibit reversible reaction chemistry leading to the formation of stoichiometric cycles driven by oxidation/reduction chemistry of the polyhedral boron-based clusters with ethelyne and dihydrogen.

Cited by 4 publications

References 34 publications

Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning

Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning

Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

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Rhodathiaborane reaction cycles driven by C2H4 and H2: synthesis and characterization of [(H)2(PPh3)RhSB8H7(PPh3)] and [(η2-C2H4)(PPh3)RhSB8H7(PPh3)]

Abstract: New 10-vertex rhodathiaboranes are reported to exhibit reversible reaction chemistry leading to the formation of stoichiometric cycles driven by oxidation/reduction chemistry of the polyhedral boron-based clusters with ethelyne and dihydrogen.

Cited by 4 publications

References 34 publications

Postsynthetic modifications of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] with Lewis bases: cluster modular tuning

Postsynthetic modifications of [2,2,2-(H)(PPh3)2-closo-2,1-RhSB8H8] with Lewis bases: cluster modular tuning

Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

Reversible Small‐Molecule Interactions with Coordinatively Unsaturated Metal Centers Held in Metallathiaborane Clusters

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Rhodathiaborane reaction cycles driven by C₂H₄ and H₂: synthesis and characterization of [(H)₂(PPh₃)RhSB₈H₇(PPh₃)] and [(η²-C₂H₄)(PPh₃)RhSB₈H₇(PPh₃)]

Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning

Postsynthetic modifications of [2,2,2-(H)(PPh₃)₂-closo-2,1-RhSB₈H₈] with Lewis bases: cluster modular tuning