Metallaborane reaction chemistry. A predicted and found tailored facile and reversible capture of SO2 by a B-frame-supported bimetallic: structures of [(PMe2Ph)2PtPd(phen)B10H10] and [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10]

Bould, Jonathan; Kennedy, John D.

doi:10.1039/b800984h

Cited by 18 publications

(8 citation statements)

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“…A more direct example showing presence of such an equilibrium is in the SO 2 adduct of [(phenanthroline)Pd(PMe 2 Ph) 2 PtB 10 H 10 ], (phen)PdPt 14 , namely, [(phenanthroline)Pd(PMe 2 Ph) 2 Pt(SO 2 )B 10 H 10 ], (phen)PdPt-SO 2 15 . Here, the 11 B spectrum of crystalline samples of (phen)PdPt-SO 2 15 dissolved in CD 2 Cl 2 shows that it forms an equilibrium mixture of 14 and 15 which requires the addition of excess SO 2 to push it to pure solutions of 15 …”

Section: Resultsmentioning

confidence: 91%

Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

et al. 2011

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Metallaborane compounds containing two adjacent metal atoms, [(PMe(2)Ph)(4)MM'B(10)H(10)] (where MM' = Pt(2), 1; PtPd, 7; Pd(2), 8), have been synthesized, and their propensity to sequester O(2), CO, and SO(2) and to then release them under pulsed and continuous irradiation are described. Only [(PMe(2)Ph)(4)Pt(2)B(10)H(10)], 1, undergoes reversible binding of O(2) to form [(PMe(2)Ph)(4)(O(2))Pt(2)B(10)H(10)] 3, but solutions of 1, 7, and 8 all quantitatively take up CO across their metal-metal vectors to form [(PMe(2)Ph)(4)(CO)Pt(2)B(10)H(10)] 4, [(PMe(2)Ph)(4)(CO)PtPdB(10)H(10)] 10, and [(PMe(2)Ph)(4)(CO)Pd(2)B(10)H(10)] 11, respectively. Crystallographically determined interatomic M-M distances and infrared CO stretching frequencies show that the CO molecule is bound progressively more weakly in the sequence {PtPt} > {PtPd} > {PdPd}. Similarly, SO(2) forms [(PMe(2)Ph)(4)(SO(2))Pt(2)B(10)H(10)] 5, [(PMe(2)Ph)(4)(SO(2))PtPdB(10)H(10)] 12, and [(PMe(2)Ph)(4)(SO(2))Pd(2)B(10)H(10)] 13 with progressively weaker binding of the SO(2) molecule. The uptake and release of gas molecules are accompanied by changes in their absorption spectra. Nanosecond transient absorption spectroscopy clearly shows that the O(2) and CO molecules are liberated from the bimetallic binding site with high quantum yields of about 0.6. For 3, in addition to dioxygen release in the triplet ground state, singlet oxygen O(2)((1)Δ(g)) was also detected with a quantum yield <0.01. In most cases, the release and rebinding of the gas molecules can be cycled with little photodegradation of the compounds. Femtosecond transient absorption spectroscopy further reveals that the photorelease of the O(2) and CO molecules, from 3 and 4 respectively, is an ultrafast process taking place on a time scale of tens of picoseconds. For SO(2), the release is even faster (<1 ps), but only in the case of mixed metal PtPd adducts, most probably because of the metal-metal bonding asymmetry in the mixed metal clusters; for the corresponding symmetric Pt(2) and Pd(2) adducts, 5 and 13, the release of SO(2) is significantly slower (>1 ns). All these compounds may have potential to serve as light-triggered local and instantaneous sources of the studied gases.

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Section: Resultsmentioning

confidence: 91%

Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

et al. 2011

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“…Among the hundreds of metallaboranes and their derivatives reported by Fehlner, Kennedy and others, − there are only a few mono- or dimetallaboranes with 12-vertices known and none with more vertices. Several approaches for the synthesis of larger clusters containing main group or transition metal fragments have received substantial attention. − The most optimum and convenient synthetic method for the construction of higher nuclearity metallaborane clusters is the condensation of metal polychlorides using [LiBH 4 ·thf], followed by the thermal expansion with [BH 3 ·thf]. , Disappointingly, in most of the cases, the great majority of metallaboranes are generated in low yield with low metal to boron ratio. , Nevertheless, applying this methodology, we have synthesized a number of new metallaboranes and their derivatives. , …”

Section: Introductionmentioning

confidence: 99%

Supraicosahedral Polyhedra in Metallaboranes: Synthesis and Structural Characterization of 12-, 15-, and 16-Vertex Rhodaboranes

et al. 2013

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Syntheses and structural characterization of supraicosahedral rhodaborane clusters are reported. Reaction of [(Cp*RhCl2)2], (Cp* = η(5)-C5Me5) with [LiBH4·thf] followed by thermolysis with excess of [BH3·thf] afforded 16-vertex closo-[(Cp*Rh)3B12H12Rh{Cp*RhB4H9}], 1, 15-vertex [(Cp*Rh)2B13H13], 2, 12-vertex [(Cp*Rh)2B10Hn(OH)m], (3a: n = 12, m = 0; 3b: n = 9, m = 1; 3c: n = 8, m = 2) and 10-vertex [(Cp*Rh)3B7H7], 4, and [(Cp*Rh)4B6H6], 5. Cluster 1 is the unprecedented 16-vertex cluster, consists of a sixteen-vertex {Rh4B12} with an exo-polyhedral {RhB4} moiety. Cluster 2 is the first example of a carbon free 15-vertex supraicosahedral metallaborane, exhibits icosihexahedron geometry (26 triangular faces) with three degree-six vertices. Clusters 3a-c have 12-vertex isocloso geometry, different from that of icosahedral one. Clusters 4 and 5 are attributed to the 10-vertex isocloso geometry based on 10-vertex bicapped square antiprism structure. In addition, quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to provide further insight into the electronic structure and stability of the optimized structures which are in satisfactory agreement with the structure determinations. All the compounds have been characterized by IR, (1)H, (11)B, (13)C NMR spectroscopy in solution, and the solid state structures were established by crystallographic analysis of compounds 1-5.

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“…On anaerobic dissolution in dichloromethane, dioxygen adduct [(PMe 2 Ph) 4 (O 2 )Pt 2 B 10 H 10 ] releases O 2 and forms an equilibrium mixture between the oxygenated and deoxygenated compounds. (SO 2 adduct [(PMe 2 Ph) 2 Pt(SO 2 )Pd(phenanthroline)B 10 H 10 ] similarly forms equilibrium mixtures …”

Section: Resultsmentioning

confidence: 99%

Ligand Lability Driven by Metal-to-Borane Pseudorotation: A Mechanism for Ligand Exchange

et al. 2020

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The discovery of systems that interact with small molecules plays a vital facilitating role in the development of devices that show sensitivity to their surroundings and an ability to quickly relay chemical and physical information. Herein, we report on the reaction of [NiCl 2 (dppe)] with decaborane that produces in usable yield a new 11-vertex nickelaborane, [7,7-(dppe)-nido-7-NiB 10 H 12 ] (1), which shows interesting reactivity and functionality toward carbon monoxide and ethylisonitrile. This contribution describes the synthesis and full structural characterization of 1 and its smallmolecule EtNC and CO adducts, 2 and 3, and delineates the dynamic molecular behavior of all of these species in solution. This information sets a foundation from which more advanced work on this and related metallaborane systems can be conceived and provides a more general reference to how NMR spectroscopy, combined with DFT calculations, can be used to analyze the precise locomotion of labile ligands around a metal center held within a borane cluster.

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Metallaborane reaction chemistry. A predicted and found tailored facile and reversible capture of SO2 by a B-frame-supported bimetallic: structures of [(PMe2Ph)2PtPd(phen)B10H10] and [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10]

Abstract: The formally closo twelve-vertex {ortho-M2B10} dimetallaborane system has been predictively tailored for reversible uptake of SO2 across the metal-metal bond, as exemplified by the formation of [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10] from [(PMe2Ph)2PtPd(phen)B10H10].

Cited by 18 publications

References 7 publications

Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects

Supraicosahedral Polyhedra in Metallaboranes: Synthesis and Structural Characterization of 12-, 15-, and 16-Vertex Rhodaboranes

Ligand Lability Driven by Metal-to-Borane Pseudorotation: A Mechanism for Ligand Exchange

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