Open, cyclic, and bicyclic compounds of double silylated phosphorus and boron

Markov, Jelena; Fischer, Roland; Wagner, Harald; Noormofidi, Nadja; Baumgartner, Judith; Marschner, Christoph

doi:10.1039/b404073b

Cited by 29 publications

(25 citation statements)

References 25 publications

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“…By reducing the known compound tBu(Hyp)PCl [9] with potassium, we were able to prepare the even bulkier diphosphane tBu(Hyp)PP(Hyp)tBu (14), which again possesses a single resonance in the 31 P NMR spectrum (Scheme 10). Xray diffraction experiments again show that it is the ,-racemic modification that is formed.…”

Section: Synthesis Of (Hypersilyl)diphosphanesmentioning

confidence: 98%

“…K. Klinkhammer even succeeded to synthesize NaSnHyp 3 , the only known compound with three hypersilyl groups on one central atom. [5] Despite this widespread use of the hypersilyl group, the number of known hypersilyl compounds of the elements of tBuHypPPHyptBu (14) was obtained. All compounds were characterized by 29 Si-and 31 P NMR spectroscopy and elemental analyses with the exception of the phosphanides which were characterized spectroscopically only.…”

Section: Introductionmentioning

confidence: 99%

“…[13] Recently, C. Marschner reported the synthesis of a bis(hypersilyl)phosphane, Hyp 2 PNR. [14] In our group, bis(trimethylsilyl)hypersilylphosphane was prepared some years ago by the reaction of bis(trimethylsilyl)lithiumphosphanide with hypersilylchloride (Scheme 1). [15] Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

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Monophosphanes and Diphosphanes with the Hypersilyl Substituent

et al. 2006

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The synthesis of (SiMe3)3SiPH2 (1) (further on denoted as hypersilylphosphane, HypPH2) was achieved by two methods: by the reaction of (SiMe3)3Si(OSO2CF3) with PH3, and alternatively, by the reaction of NaPH2 with (SiMe3)3SiCl (hypersilylchloride). The latter reaction also afforded bis(hypersilyl)phosphane Hyp2PH (2). By the reaction of 1 and known hypersilylbis(trimethylsilyl)phosphane (3) with tBuOK, the novel hypersilylphosphanides HypPHK (4) and Hyp(SiMe3)PK (5) were prepared. Compound 1 also reacted with nBuLi to form HypPHLi (6) and HypPLi2 (7). Furthermore, 3 reacted with hexachloroethane and 1,2‐dibromotetrachloroethane to give HypPCl(SiMe3) (8) and HypPBr(SiMe3) (9) as well as HypPCl2 (10) and HypPBr2 (11). Compounds 4 and 5 reacted smoothly with 1,2‐dibromoethane to give diphosphane HypHPPHHyp (12) as a mixture of the meso‐ and rac‐d,l‐diastereomers and Hyp(SiMe3)PP(SiMe3)Hyp (13) as the d,l‐modification only. By reducing the known compound tBuHypPCl with potassium, the d,l‐modification of tBuHypPPHyptBu (14) was obtained. All compounds were characterized by 29Si‐ and 31P NMR spectroscopy and elemental analyses with the exception of the phosphanides which were characterized spectroscopically only. The crystal structures of 3 and 4 and of diphosphanes 10, 11 and 13 are reported. From temperature‐dependent 31P NMR experiments, the coalescence temperature for the meso↔d,l interconversion of 12 was determined at 110 °C and gave an inversion barrier of roughly 69.4 kJ mol–1, which is corroborated by results of ab initio calculations at the B3LYP/6‐31G(d) level. Two diastereomeric inversion transition structures for diphosphanes R–PH–PH–R with either a syn or an anti arrangement of the P–H bond and the phosphorus lone pair of electrons could be located; bulky substituents seem to prefer the anti arrangement.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Synthesis Of (Hypersilyl)diphosphanesmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Monophosphanes and Diphosphanes with the Hypersilyl Substituent

et al. 2006

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“…Over the past years, we have utilized oligosilanylene diides 1−4 for the synthesis of longer oligosilane chains, 5−10 cyclosilanes, 2,7,11−14 heterocyclosilanes, 11,12,15,16 and as ligands for silyl transition metal complexes 1,4,17−22 and silylated low valent main group compounds. 23−30…”

Section: Introductionmentioning

confidence: 99%

Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

2019

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Synthesis of a number of disiloxane containing cyclo- and bicyclooligosilanes is described starting from the dipotassium 1,5-oligosiloxanylene diide derived from 1,3-bis[tris(trimethylsilyl)silyl]tetramethyldisiloxane. In addition, the use of this particular fragment as ligand for zinc and group 4 metallocene complexes was studied. Both types of compounds exhibit marked structural differences compared to related compounds containing Si-Si-Si units instead of the Si-O-Si fragment.

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“… 2 With respect to group 15 compounds, however, this was limited to a single study demonstrating the availability of phosphacyclo- and bicyclosilanes. 10 The current account intends to show how oligosilanyl anion chemistry can be used to establish some foundations of oligosilanylstibine chemistry.…”

Section: Introductionmentioning

confidence: 99%

Oligosilanylated Antimony Compounds

Zitz¹,

Gatterer²,

Reinhold

et al. 2015

Organometallics

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By reactions of magnesium oligosilanides with SbCl3, a number of oligosilanylated antimony compounds were obtained. When oligosilanyl dianions were used, either the expected cyclic disilylated halostibine was obtained or alternatively the formation of a distibine was observed. Deliberate formation of the distibine from the disilylated halostibine was achieved by reductive coupling with C8K. Computational studies of Sb–Sb bond energies, barriers of pyramidal inversion at Sb, and the conformational behavior of distibines provided insight for the understanding of the spectroscopic properties.

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Open, cyclic, and bicyclic compounds of double silylated phosphorus and boron

Cited by 29 publications

References 25 publications

Monophosphanes and Diphosphanes with the Hypersilyl Substituent

Monophosphanes and Diphosphanes with the Hypersilyl Substituent

Chemistry of a 1,5-Oligosilanylene Dianion Containing a Disiloxane Unit

Oligosilanylated Antimony Compounds

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