A Novel Hexamer of Bu<i>t</i>C  P: Synthesis, Structure, and Theoretical Studies

Caliman, Vinicius; Hitchcock, Peter B.; Nixon, John F.; Hofmann, Matthias; Schleyer, Paul von Ragué

doi:10.1002/anie.199422021

Cited by 47 publications

(17 citation statements)

References 19 publications

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“…2 Longer COP bonds and the lack of pendant organic groups attached to phosphorus make phosphaalkynes potential precursors to conjugated polymers. However, few details concerning their polymerization chemistry are known, save that t-butylphosphaethyne and a few other sterically stabilized phosphaalkynes undergo thermally induced (130 -180°C) 3 or Lewis acid-mediated cycloaddition reactions 4 -9 to give polyhedral oligomers (primarily the tetramer, but the hexamer has also been isolated) 7 rather than linear oligomers or polymers. Spontaneous "polymerization" reactions of phosphaalkynes with less sterically demanding substituents (RAH, CH 3 , Me 3 Si, phenyl) have also been reported, 10 -13 but none of the products have been characterized.…”

Section: Introductionmentioning

confidence: 99%

Spontaneous polymerization of phenylphosphaethyne

Loy

Jamison

McClain

et al. 1999

J. Polym. Sci. A Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

Spontaneous polymerization of phenylphosphaethyne

Loy

Jamison

McClain

et al. 1999

J. Polym. Sci. A Polym. Chem.

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“…[7] Phosphaalkynes can be oligomerized with the aid of metal organic reagents or Lewis acids, [8] and the zirconocenemediated tetramerization of phosphaalkynes is the route of choice for the high-yield preparation of tetraphosphacubane derivatives. [9] Other saturated cage compounds such as pentameric tBu 5 C 5 P 5 [10] and the hexameric tBu 6 C 6 P 6 [11] have been described by us by coupling reactions of the tBu 2 C 2 P 3 and tBu 3 C 3 P 2 ring systems, as well as partially unsaturated cages formed by the reaction of highly reactive arene iron(0) complexes with tert-butylphosphaalkyne (3). [12] Results and Discussion…”

Section: Introductionmentioning

confidence: 99%

“…In this paper we describe the formation of a novel hexaphosphapentaprismane derivative tBu 4 C 4 P 6 2, which can be prepared either by light-induced valence isomerization of an unsaturated precursor tBu 4 C 4 P 6 1 or by metal elimination of the remarkable trimeric mercury complex [(tBu 4 C 4 P 6 )Hg] 3 (11). Both 1 and 2 open a new gateway to organophosphorus cage chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Hexaphosphapentaprismane: A New Gateway to Organophosphorus Cage Compound Chemistry

Al-Ktaifani

Bauer

Bergsträßer

et al. 2002

Chemistry A European J

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Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light‐induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis‐[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single‐crystal X‐ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13.

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“…9 A clear chemical difference between the P 2 C 10 and P 6 C 6 units is the presence of unsaturated CLC bonds in 1-3 whereas P 6 C 6 Bu t 6 contains formally saturated, P-P, P-C and C-C contacts; presumably this is on account of the higher reactivity of PLC vs. CLC, leading to the more open structures of 1-3.…”

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The surprising and stereoselective formation of P2C10 cages by the reduction of Cp*PCl2

et al. 2006

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Reactions of Cp*PCl 2 with Group 13 reducing agents result in a cascade of P-C, P-P and C-C bond forming reactions and the stereoselective formation of P 2 C 10 cages.The last decade has witnessed spectacular advances in molecular main group cluster chemistry. Amongst the most eye catching have been the metalloid type clusters containing [Al 77 [1][2][3] In parallel, important milestones have been reached in phosphoruscarbon clusters which have been synthesised with various P : C ratios, and which have been shown to possess fascinating coordination chemistry; 4-6 the synthesis of such clusters often involves phosphaalkynes as a starting point which limits the general accessibility of the materials. As part of our ongoing studies towards synthesising cage complexes containing the p-block elements, 7,8 we have discovered facile syntheses of elaborate P 2 C 10 cages, both as a neutral species and as part of a cation, by reductive coupling of Cp*PCl 2 using Group 13 reagents.The cations of 1 and 2 were synthesised in quantitative yield{ by stirring solutions of MX (Scheme 1; M = Ga, X = I, 1; M = In, X = Cl, 2) with Cp*PCl 2 at room temperature for 30 minutes; the compounds formed colourless crystals upon layering chlorinated solutions of the compounds with hexane. § The neutral compound 3 was synthesized by reacting a toluene solution of Cp*PCl 2 with excess gallium metal at 50 uC for 10 days and could be isolated in 78% yield.Single crystal X-ray crystallographic studies showed the molecular structures of 1 and 2 to be isomorphous, consisting of ion-separated [MX 4 ] 2 anions and cationic cages of molecular C 1 symmetry comprising two P centres (one of which is ligated by a halogen atom) and ten CMe units (see Fig. 1 for a diagram of the cationic unit of 1). In both cations, the two phosphorus atoms are joined by a single bond {P(1)-P(2) 2.178(6) in 1; 2.153(2) s in 2}, two of the C-C contacts are formally unsaturated {C(1)-C(5) 1.36(2), C(8)-C(9) 1.36(2) in 1; C(1)-C(5) 1.346(7), C(8)-C(9) 1.340(7) s in 2} whereas the remainder are saturated. It should be noted that several of the C-C single bonds are rather longer than normal C-C bonds {up to 1.64(2) s}, presumably on account of the high degree of steric crowding and the imposed tight bond angles {as acute as 88.6(8)u} in the cations. Both phosphorus atoms and the six saturated carbon centres are formally chiral, and in addition, the cation possesses a helical twist. In this respect, it is of note that both 1 and 2 crystallised in chiral space groups (P2 1 and P2 1 2 1 2 1 for 1 and 2 respectively). For 1, each individual crystal represents a single enantiomer, although the overall mixture contains a mixture of two enantiomers; in contrast, 2 crystallises as a racemic twin. The observation of just one enantiomeric pair from the many possible combinations is presumably a manifestation of both the reaction pathway to form the P 2 C 10 units and the geometric constraints of the cage. In contrast to the cationic cages 1 and 2 the neutral compound 3 crystallises ...

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A Novel Hexamer of ButC  P: Synthesis, Structure, and Theoretical Studies

Cited by 47 publications

References 19 publications

Spontaneous polymerization of phenylphosphaethyne

Spontaneous polymerization of phenylphosphaethyne

Hexaphosphapentaprismane: A New Gateway to Organophosphorus Cage Compound Chemistry

The surprising and stereoselective formation of P2C10 cages by the reduction of Cp*PCl2

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