Synthesis of Aminophosphane Complexes: Searching the Boundary between Phosphanide and Phosphinidenoid Complex Chemistry

Duan, Lili; Schnakenburg, Gregor; Daniels, Jörg; Streubel, Rainer

doi:10.1002/ejic.201101437

Cited by 11 publications

(11 citation statements)

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“…A similar trend was also observed in case of P−CH(SiMe 3 ) 2 derivatives. 17 Almost unaffected of the substituents at nitrogen are the tungsten−phosphorus ( 1 J W,P = 254−259 Hz) and the phosphorus−hydrogen coupling constant magnitudes ( 1 J P,H = 346−354 Hz). The ν(P−H) stretching vibrations of 3−10 are found in the IR spectra between 2296 and 2365 cm −1 which is in agreement with reported values.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The 31 P NMR spectrum of the reaction mixture revealed three signals at 159.9 ppm (10%), 79.2 ppm (57%) (17), and 49.2 ppm (33%). The latter signal corresponds to the starting material ( 5), probably reformed by hydrogen atom abstraction.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…16a By comparison, the Li/NR 2 and Na/NR 2 tungsten(0) complexes having the same substituent at the phosphorus center suffered from decomposition in solution. 17 Very recently, the first synthesis of a K/N(H)R phosphinidenoid complex by deprotonation of the corresponding aminophosphane complex with KHMDS in the presence of 18-crown-6 was published. 18 In the same study, synthesis of an azadiphosphiridine complex with PhPCl 2 using deprotonation conditions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In contrast, Li/OR and Li/NR 2 phosphinidenoid tungsten(0) complexes are much less investigated, and their reactivity has been scarcely explored. For example, Li/OR phosphinidenoid tungsten(0) complexes revealed a higher thermal stability than their Li/Cl counterparts .…”

Section: Introductionmentioning

confidence: 99%

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1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

et al. 2017

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Syntheses of 1,1′-bifunctional aminophosphane complexes 3–10 was achieved by reacting Li/Cl phosphinidenoid complex 2 (R = CPh3) with secondary (Me2NH, Et2NH, Bn2NH, pyrrolidine, and piperidine), primary amines (EtNH2 and allyl amine), and ammonia. Furthermore, regioselective N-silylation of 11 (R = Me) was achieved using MeLi and Me3SiCl to give complex 12. In contrast, treatment of complex 6 with KHMDS in the presence of 18-crown-6 yielded K/NMe2 phosphinidenoid complex 13 subsequently reacted with MeI to give P–Me substituted 14. Complex 5 was deprotonated with KHMDS in the presence of 18-crown-6 and reacted with [Ph3C]BF4 to yield complex 17 via single-electron transfer reaction and P,C-heterocoupling. Finally, selective P–N bond cleavage was achieved by treating complex 18 (R = t-Bu) with HCl(g) to afford chlorophosphane complex 19.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

et al. 2017

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“…Li/OR phosphinidenoid tungsten(0) complexes display a higher thermal stability than their chloro counterparts, which can be enhanced by cation encapsulation to form the cation [Li(12‐crown‐4) 2 ] + . In contrast, Li/NR 2 and Na/NR 2 tungsten(0) complexes that bear the same phosphorus substituent suffered from decomposition in solution …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P₂N‐Ring Ligand

Majhi

Kyri

Schmer

et al. 2016

Chemistry A European J

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Synthesis of 1,1'-bifunctional aminophosphane complexes 3 a-e was achieved by the reaction of Li/Cl phosphinidenoid complex 2 with various primary amines (R=Me, iPr, tBu, Cy, Ph). Deprotonation of complex 3 a (R=Me) with potassium hexamethyldisilazide yielded a mixture of K/NHMe phosphinidenoid complex 4 a and potassium phosphanylamido complex 4 a'. Treatment of complex 3 c (R=tBu) and e (R=Ph) with KHMDS afforded the first examples of K/NHR phosphinidenoid complexes 4 c and e. The reaction of complex 3 c with 2 molar equivalents of KHMDS followed by PhPCl afforded complexes 5 c,c', which possess a P N-ring ligand. All complexes were characterized by NMR, IR, MS, and microanalysis, and additionally, complexes 3 b-e and 5 c' were scrutinized by single-crystal X-ray crystallography.

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Application of Imidazole‐2‐thione Substituents in Low‐Coordinate Phosphorus Chemistry – Probing the Scope

et al. 2016

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A variety of (2-thioxoimidazol-4-yl)phosphanes have been synthesized with the prospect of further functionalization. Following a standard reaction protocol, P-amino (2a,b), P-chloro (3a,b), and P-hydrogeno (8a) phosphane derivatives were synthesized. Treatment of chlorophosphanes 3a,b with Lewis acids in dichloromethane/diethyl ether did not afford the expected phosphenium cation, instead ethoxyphosphane derivatives 5a,b were isolated. Treatment of secondary phosphane 8a with potassium hexamethyldisilazide afforded 2-thioxoimidazol-4-ylsubstituted phosphanide derivative 10a, which was used to access dinuclear phosphanido borane 11a and tungsten com- [a] 3563 Scheme 4. Synthesis of ligand-stabilized phosphenium cations 6b and 7b.represented as a phosphanylphosphonium cation. [31] The 31 Eur.

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Synthesis of Aminophosphane Complexes: Searching the Boundary between Phosphanide and Phosphinidenoid Complex Chemistry

Cited by 11 publications

References 39 publications

1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P₂N‐Ring Ligand

Application of Imidazole‐2‐thione Substituents in Low‐Coordinate Phosphorus Chemistry – Probing the Scope

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Synthesis of Aminophosphane Complexes: Searching the Boundary between Phosphanide and Phosphinidenoid Complex Chemistry

Cited by 11 publications

References 39 publications

1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

1,1′-Bifunctional Aminophosphane Complexes via N–H Bond Insertions of a Li/Cl Phosphinidenoid Complex and First Studies on N/P Mono Functionalizations

Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P2N‐Ring Ligand

Application of Imidazole‐2‐thione Substituents in Low‐Coordinate Phosphorus Chemistry – Probing the Scope

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Synthesis and Deprotonation of Aminophosphane Complexes: First K/N(H)R Phosphinidenoid Complexes and Access to a Complex with a P₂N‐Ring Ligand