Phosphaborane chemistry. Syntheses and calculated molecular structures of mono- and di-chloro derivatives of 1,2-diphospha-closo-dodecaborane(10)

Grüner, Bohumı́r; Hnyk, Drahomı́r; Cı́sařová, Ivana; Plzák, Zbyněk; Štı́br, Bohumil

doi:10.1039/b201086k

Cited by 16 publications

(25 citation statements)

References 28 publications

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“…The neutral compound 7,8,9-PC 2 B 8 H 11 (2) and its chlorinated derivative 10-Cl-2 can now easily be prepared by phosphorus insertion from the readily available 5,6-C 2 B 8 H 12 (1) dicarbaborane. [6] We have demonstrated that the constitution of 2 is analogous to that of the neutral tricarbollide 7,8,9-C 2 B 8 H 12 (3) as the bare P vertex is isolobal with the cage CH group.…”

Section: Discussionmentioning

confidence: 99%

“…Moreover, these pentagons are not planar, as exemplified by some dihedral angles in Table 1, although such a nonplanarity is less marked in the neutral species. As found in other phosphaboranes, [7,11] the Cl-substitution brings about only marginal effects in the molecular cage geometry relative to an unsubstituted compound (see Table 1). The PϪC, PϪB, CϪC, and BϪB nearest-neighbor separations in the open pentagonal belts resemble those determined for the four P 2 C 2 B 7 H 9 isomers and their Cl derivatives [7] , at the same level of theory [e.g.…”

Section: Geometry Optimizationmentioning

confidence: 99%

“…The 31 P NMR spectra of all compounds show one singlet and the 13 C NMR spectra display one doublet ( 1 J PϪC splitting) and one broader singlet (with fine multiplet 1 J CB splitting) due to C(8) and C(9) resonances, respectively. As in the 11 ] ppm) resonances, in the corresponding 1 H and 13 C (data in square brackets) NMR spectra of anions 2 ؊ and 10-Cl-2 ؊ , with respect to those of the neutral 2 and 10-Cl-2. This effect is copied in the 31 P NMR spectra in which the singlet resonances of the anionic species 2 ؊ and 10-Cl-2 ؊ again exhibit shielding (∆δ ϭ 33.1 and 27.7 ppm) with respect to those of the neutral compounds 2 and 10-Cl-2.…”

Section: Nmr Spectroscopic Studiesmentioning

confidence: 99%

“…[1] Recent efforts are dominated by successful attempts at the isolation of phoshacarborane analogues of tricarbollides (11-vertex nido-tricarbaboranes). [2] In this field of chemistry, one of our groups has recently reported preliminary results on the synthesis of the nido-phosphadicarbaboranes 7,8,11-PC 2 B 8 H 11 and [7,8,11-PC 2 B 8 H 10 ] Ϫ based on the reaction between [6,9-C 2 B 8 H 10 ] 2Ϫ and PCl 3 . [3] The first species is an analog of the neutral tricarbollide 7,8,9-C 3 B 8 H 12 and the second anion is analogous to [7,8,9-C 3 B 8 H 11 ] Ϫ .…”

Section: Introductionmentioning

confidence: 99%

“…[3] The first species is an analog of the neutral tricarbollide 7,8,9-C 3 B 8 H 12 and the second anion is analogous to [7,8,9-C 3 B 8 H 11 ] Ϫ . [4] Both anions, [7,8,11-PC 2 B 8 H 10 ] Ϫ and [7,8,9-C 3 B 8 H 11 ] Ϫ are also regarded [2] as perfect Cp analogs as they are monoanionic and contain an ab initio methods at a correlated level of theory [RMP2(fc)] using the 6-31G* basis set and their correctness was assessed by a comparison of the experimental 11 B NMR chemical shifts with those calculated by the GIAO-SCF/II//RMP2(fc)/ 6-31G* method. Moreover, the structure of 10-Cl-2 − was determined by an X-ray diffraction analysis.…”

Section: Introductionmentioning

confidence: 99%

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Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranesnido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]−, and Their 10-Cl Derivatives − Analogs of the Cyclopentadienide Anion

Štı́br

Holub

Bakardjiev

et al. 2002

Eur. J. Inorg. Chem.

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The reaction of the carborane nido‐5,6‐C2B8H12 (1) with PCl3 in dichloromethane in the presence of a “proton sponge” [PS = 1,8‐bis(dimethylamino)naphthalene], followed by hydrolysis of the reaction mixture, resulted in the isolation of the eleven‐vertex nido‐phosphadicarbaboranes 7,8,9‐PC2B8H11 (2) and 10‐Cl‐7,8,9‐PC2B8H10 (10‐Cl‐2), depending on the ratio of the reactants. Both of these compounds can be deprotonated by PS to give the nido anions [7,8,9‐PC2B8H10]− (2−) and [10‐Cl‐7,8,9‐PC2B8H9]− (10‐Cl‐2−). The molecular geometries of all compounds were optimized by ab initio methods at a correlated level of theory [RMP2(fc)] using the 6‐31G* basis set and their correctness was assessed by a comparison of the experimental 11B NMR chemical shifts with those calculated by the GIAO‐SCF/II//RMP2(fc)/6‐31G* method. Moreover, the structure of 10‐Cl‐2− was determined by an X‐ray diffraction analysis. The anionic compounds 2− and 10‐Cl‐2− are analogs of the Cp (Cp = η5‐C5H5−) anion. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Discussionmentioning

confidence: 99%

Section: Geometry Optimizationmentioning

confidence: 99%

Section: Nmr Spectroscopic Studiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranesnido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]−, and Their 10-Cl Derivatives − Analogs of the Cyclopentadienide Anion

Štı́br

Holub

Bakardjiev

et al. 2002

Eur. J. Inorg. Chem.

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Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Kelly

2005

Encyclopedia of Inorganic Chemistry

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The element phosphorus was first discovered in 1669, and some measure of the growth of its uses and importance since then is evident from the fact that approximately half a million tons of the element are now produced annually; in addition, phosphorus‐based materials may be generated from naturally occurring phosphates, and for this reason over 130 million tons of such material are utilized per annum. Its importance to life means that natural phosphorus cycles occur; in addition, utilization of the element and its compounds is key to many industrial processes (producing products varying from pesticides to oil additives). In the laboratory, work has shown that many ‘naked’ phosphide anions can be prepared – these can even mimic organic systems, as in the case of the cyclo [P 5 ] − ligand, which binds face on to metals in the manner of the cylcopentadienyl ligand. In addition, there are many examples of transition metal complexes of ligands containing only phosphorus; these range in size from just a single phosphorus atom to complex structures containing up to 14 atoms. Away from transition metal chemistry, phosphorus forms compounds with elements from all groups of the periodic table barring the noble gases; this article provides an overview of such compounds, with special interest in compounds that have an industrial use, that stabilize unusual bonding arrangements, or that are of current interest. In the process, it highlights the ability of the element to become involved in catenation and to form small cluster units, often with many PP bonds present. Thus, group 13 compounds of the element include the industrially important phosphides and a recently prepared new class of boron–phosphorus polymer. Silicon compounds of the element often exhibit unusual structures and some of these are illustrated and reference is made to multiple‐bonded systems, including the first example of a phosphabismuthene. Sulfides such as P 4 S 10 and halides such as PCl 3 and POCl 3 are of immense industrial importance and details of such processes and the consumption levels are provided. References to recent reviews on a range of pertinent topics are provided, including PSi chemistry, phosphides, phosphorus‐based polymers, phosphorus complexes of transition metals, phosphorus‐borane chemistry, phosphane ligands, organophosphorus chemistry, and phosphorus hydrides.

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Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Kelly

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Phosphaborane chemistry. Syntheses and calculated molecular structures of mono- and di-chloro derivatives of 1,2-diphospha-closo-dodecaborane(10)

Cited by 16 publications

References 28 publications

Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranesnido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]−, and Their 10-Cl Derivatives − Analogs of the Cyclopentadienide Anion

Phosphacarborane Chemistry: The Synthesis of the Parent Phosphadicarbaboranesnido-7,8,9-PC2B8H11 and [nido-7,8,9-PC2B8H10]−, and Their 10-Cl Derivatives − Analogs of the Cyclopentadienide Anion

Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Phosphorus: Inorganic ChemistryBased in part on the article Phosphorus: Inorganic Chemistry by Josef Novosad which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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