Synthese, spektroskopische Charakterisierung und Molekülstrukturen ausgewählter Lewis‐Basen‐Addukte der Alkalimetall‐tri(tert‐butyl)silylphosphanide

Westerhausen, Matthias; Weinrich, Sabine; Schmid, Bertram; Schneiderbauer, Stefan; Suter, Max; Nöth, Heinrich; Piotrowski, Holger

doi:10.1002/zaac.200390106

Cited by 24 publications

(15 citation statements)

References 53 publications

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“…The central unit of the observed potassium complexes is formed by the metal cation and the surrounding crown ether ligand, with bond lengths between potassium and oxygen ranging from 2.7750(19) (K2-O13) to 2.9212(17) Å (K1-O5), which is consistent with related complexes. [28,29] The diphosphanylmethanide ligands show unsymmetrical κ 2 PP coordination modes, with distances between 3.4952(9) and 3.884(1) Å. An increase of the average distance between potassium and phosphorus to 3.657 Å (relative to 5, see Table 1) indicates a higher degree of steric pressure at the metal center in the solid state.…”

Section: Ch]mentioning

confidence: 96%

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

2014

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The reaction of [K{(Ph2P)2CH}(Et2O)0.5]n with an excess of tetrahydropyran yields polymeric [K{(Ph2P)2CH}(thp)]∞ (1). Application of neutral bidentate ligands such as dimethoxyethane or N,N,N′N′‐tetramethylethylenediamine leads to a splitting of the polymeric starting material into discrete dinuclear entities and the complexes [K{(Ph2P)2CH}(dme)]2 (3) and [K{(Ph2P)2CH}(tmeda)]2 (4) were isolated. In compounds 1, 3 and 4, the phosphorus atoms as well as the methanide carbon atom and two of the four phenyl groups of the anionic ligand participate in metal binding. Oligodentate ligands such as diglyme and 18‐crown‐6 enforce a reduction of the interaction between potassium and the diphosphanylmethanide anion and lead to the mononuclear complexes [K{(Ph2P)2CH}(diglyme)2] (5) and [{K{(Ph2P)2CH}(18C6)}{K{(Ph2P)2CH}(18C6)(thf)}] (6), respectively. In these compounds, only the phosphorus atoms of the diphosphanylmethanide ligands coordinate to the central potassium cation. The related lithium derivative [Li{(Ph2P)2CH}(thp)3] (2) was prepared for comparison. All complexes were characterized by NMR methods and X‐ray diffraction measurements.

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Section: Ch]mentioning

confidence: 96%

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

2014

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“…Structural reports for potassium phosphanides are available for a small number of compounds only. Examples are K(thf)P(SiMe 3 ) 2 , which displays a ladder-type structure, [22] KHPSitBu 3 , [34] polymeric KHPMes* (Mes* = 2,4,6-tBu 3 C 6 H 12 ) [35] and dimeric [K(thf) 2 P(2,4,6-Me 3 C 6 H 2 )SiFtBu 2 ] 2 . [36] Because of the large size of the hypersilyl group and the presence of 18-crown-6, each phosphorus atom in 4 is coordinated to one potassium atom only, which is different from the above-mentioned examples where coordination numbers two or three are observed.…”

Section: X-ray Crystallographymentioning

confidence: 99%

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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“…Whereas the metallation of tri(tert-butyl)silylphosphane has already been reported, [23] there are no reports on the homologous arsane. The metathesis reaction of [(dme)LiAsH 2 ] with tBu 3 SiO 3 SCF 3 in DME yields tri(tert-butyl)silylarsane (1) and lithium trifluoromethanesulfonate in large quantities according to Equation (1).…”

Section: Synthesis and Nmr Spectroscopymentioning

confidence: 97%

The Influence of the Neutral Coligand on the Spectroscopic Properties and Crystal Structures of Lithium Tri(tert‐butyl)silylarsanides of the Type[(L)LiAs(H)SitBu₃] (L = DME, THF)

et al. 2005

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The reaction of [(dme)LiAsH 2 ] with F 3 CSO 3 SitBu 3 yields tri-(tert-butyl)silylarsane (1). The reaction of 1 with n-butyllithium in 1,2-dimethoxyethane gives [(dme)LiAs(H)SitBu 3 ] 2 (2), whereas the lithiation of 1 in THF leads to the formation of the one-dimensional polymer [(THF)LiAs(H)SitBu 3 ] ϱ (3). The Li-As bond lengths of both of these compounds show a similar value of approximately 260 pm. However, the smaller co-

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Synthese, spektroskopische Charakterisierung und Molekülstrukturen ausgewählter Lewis‐Basen‐Addukte der Alkalimetall‐tri(tert‐butyl)silylphosphanide

Cited by 24 publications

References 53 publications

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

Monophosphanes and Diphosphanes with the Hypersilyl Substituent

The Influence of the Neutral Coligand on the Spectroscopic Properties and Crystal Structures of Lithium Tri(tert‐butyl)silylarsanides of the Type[(L)LiAs(H)SitBu₃] (L = DME, THF)

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Synthese, spektroskopische Charakterisierung und Molekülstrukturen ausgewählter Lewis‐Basen‐Addukte der Alkalimetall‐tri(tert‐butyl)silylphosphanide

Cited by 24 publications

References 53 publications

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

Syntheses and Structures of Potassium Complexes Containing Bis(diphenylphosphanyl)methanide Anions

Monophosphanes and Diphosphanes with the Hypersilyl Substituent

The Influence of the Neutral Coligand on the Spectroscopic Properties and Crystal Structures of Lithium Tri(tert‐butyl)silylarsanides of the Type[(L)LiAs(H)SitBu3] (L = DME, THF)

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The Influence of the Neutral Coligand on the Spectroscopic Properties and Crystal Structures of Lithium Tri(tert‐butyl)silylarsanides of the Type[(L)LiAs(H)SitBu₃] (L = DME, THF)