From Racemic Primary Aminoalkyl(phosphanyl)ferrocene Complexes to a Lithium–Phosphorus <i>closo</i> Cluster

Tschirschwitz, Steffen; Lönnecke, Peter; Reinhold, J.; Hey‐Hawkins, Evamarie

doi:10.1002/anie.200462543

Cited by 14 publications

(9 citation statements)

References 37 publications

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“…Thus, compounds 5 and 6 were obtained by reaction of crude 3 or 4 with LiAlH 4 (Scheme 1) in shorter time and much better yield than reported by us previously. 14 Phosphane 6 is a crystalline solid whose structure is depicted in Fig. 4.…”

Section: Resultsmentioning

confidence: 99%

“…We have already shown that 5 can be lithiated twice and that the resulting dilithium phosphanediide forms a hexameric aggregate with a central Li 12 P 6 unit which can be described as a closo cluster. 14 To extend this chemistry, a similar reaction was performed with (R,S)-9 as starting material.…”

Section: Resultsmentioning

confidence: 99%

“…In addition to the known phosphanylferrocene 12 and 1,1 -bis(phosphanyl)ferrocene, 13 we recently reported on the synthesis of primary aminoalkylferrocenylphosphanes by reduction of the corresponding ferrocenylphosphonates. 14 We showed that racemic 2-(N,N-dimethylaminomethyl)phosphanylferrocene (5) can easily be dilithiated. The resulting dilithium phosphanediide crystallises as a hexamer containing all-R-or all-S-configured units with a central Li 12 P 6 cluster, which, according to theoretical studies, can be described as a closo cluster according to Wade's rules.…”

Section: Introductionmentioning

confidence: 99%

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Aminoalkylferrocenyldichlorophosphanes: facile synthesis of versatile chiral starting materials

2007

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A series of racemic and optically pure aminoalkylferrocenyldichlorophosphanes has been prepared by reaction of phosphorus trichloride with the corresponding lithiated aminoalkylferrocene precursors. Crystal structures of racemic 1-dichlorophosphanyl-2-N,N-dimethylaminomethylferrocene, racemic 1-dichlorophosphanyl-2-N,N-dimethylaminomethyl-3-triphenylsilylferrocene and (S)-N,N-dimethyl-1-[(R)-2-(dichlorophosphanyl)ferrocenyl]ethylamine reveal short intramolecular N[dot dot dot]P distances, which are suggestive of weak N --> P dative bonds. The aminoalkylferrocenyldichlorophosphanes can be used for the preparation of the corresponding primary phosphanes, one of which was characterised by X-ray crystallography. Optically pure (R)-N,N-dimethyl-1-[(S)-2-(phosphanyl)ferrocenyl]ethylamine can easily be lithiated twice to give the first enantiomerically pure lithium-phosphorus closo cluster compound, which was also structurally characterised.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Aminoalkylferrocenyldichlorophosphanes: facile synthesis of versatile chiral starting materials

2007

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“…BH 3 (THF) (1 M in THF) was purchased and purified by bulb‐to‐bulb vacuum distillation before use. [Fe(C 5 H 5 ){C 5 H 3 (CH 2 NMe 2 )PH 2 }],17b [{Rh(μ‐Cl)(cod)} 2 ],38 [FcCH 2 PH 2 ],39 [FcPH 2 ],40 and [FcCH 2 PH 2 (BH 3 )]20 were synthesized according to literature procedures. NMR spectra were recorded with a Bruker AVANCE DRX 400 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Phosphorus–Boron‐Based Polymers Obtained by Dehydrocoupling of Ferrocenylphosphine–Borane Adducts

2014

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Dehydrocoupling of the ferrocenylphosphine-borane adducts [FcPH 2 (BH 3 )] (1) [Fc = Fe(C 5 H 5 )(C 5 H 4 )] and [FcCH 2 PH 2 (BH 3 )] (2) with [{Rh(μ-Cl)(cod)} 2 ] (cod = 1,5-cyclooctadiene) as catalyst gave the corresponding phosphorusboron-based polymers [FcPH(BH 2 )] n (3) and [FcCH 2 -PH(BH 2 )] n (4) as low-(heating in toluene, 3 low and 4 low ) or high-molecular-weight (heating without solvent, 3 high or 4 high ) poly(ferrocenylphosphinoborane)s depending on the reaction conditions. Dehydrocoupling of a racemic mixture of [2-N,N-dimethyl(N-borane)aminomethyl-1-ferrocenyl]phosphine-borane (6) resulted in several products, as both BH 3 moieties are apparently involved in polymer formation. Quaternization of the amino group in planar-chiral [Fe(C 5 H 5 ){C 5 H 3 (CH 2 NMe 2 )PH 2 }] (5) with MeI and treatment of the corresponding ammonium salt [Fe(C 5 H 5 )- [a]2457 bond angles at phosphorus vary from 99.6(1) to 115.5(7)°, and those at boron from 102.7(1) to 113.9(2)°.

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“…Only some larger derivatives, mostly containing lithium,a re known in the literature. [38,40,[46][47][48][49][50][51][52][53][54][55][56][57] In contrast to compound 5,t he coordination number of the phosphorus atom in 6 increases to five. The potassium atoms coordinated by two phosphorus atoms (K1 and K1')h aveac oordination number of six (2 P, 2 O, 2 CH 3 agostici nteraction with the methyl groups of the tBu substituents), whereas the potassium atoms solely coordinated by one phosphorusa tom show one agostici nteraction to am ethyl group (K2, K2',K 3, and K3').…”

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confidence: 99%

Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters

Balmer

Weigend

Hänisch

2019

Chemistry A European J

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The N‐heterocyclic carbene (NHC)‐stabilized phosphinidenide, SIMesPK [SIMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolidine‐2‐ylidene], was used as an (NHC)P‐transfer reagent for the synthesis of the low‐valent Group 14 ate complexes K[(SIMesP)3E] (E=Ge: 2, Sn: 3, Pb: 4), which were characterized by 1H NMR, 31P NMR, IR spectroscopy as well as elemental and X‐ray analysis. Furthermore, SIMesPK was used in reactions with potassium amides and alkoxides to form the molecular phosphorus–potassium clusters [K4(SIMesP)2(hmds)2] [5, hmds=N(SiMe3)2] and [K6(SIMesP)2(OtBu)4] (6). Finally, the reaction of SIMesPK with Li[Al(OC4F9)4] led to the potassium‐rich ionic compound [(SIMesP)4K5][Al(OC4F9)4] (7).

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From Racemic Primary Aminoalkyl(phosphanyl)ferrocene Complexes to a Lithium–Phosphorus closo Cluster

Cited by 14 publications

References 37 publications

Aminoalkylferrocenyldichlorophosphanes: facile synthesis of versatile chiral starting materials

Aminoalkylferrocenyldichlorophosphanes: facile synthesis of versatile chiral starting materials

Phosphorus–Boron‐Based Polymers Obtained by Dehydrocoupling of Ferrocenylphosphine–Borane Adducts

Low‐Valent Group 14 NHC‐Stabilized Phosphinidenide ate Complexes and NHC‐Stabilized K/P‐Clusters

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