Synthese und Eigenschaften teilsilylierter Tri‐ und Tetraphosphane. Reaktionen lithiierter Diphosphane mit Chlorphosphanen

Fritz, Florian; Vaahs, T.

doi:10.1002/zaac.19875520904

Cited by 39 publications

(12 citation statements)

References 15 publications

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“…According to 31 P NMR spectroscopy the reaction of t Bu 2 P–P(SiMe 3 )Li with [ Me NacnacTiCl 3 ] in molar ratio 1:1 in toluene- d 8 (NMR tube) does not lead to the formation of a putative phosphanylphosphido Ti IV complex [ Me NacnacTiCl 2 {η 1 -P(SiMe 3 )-P t Bu 2 }] nor to [ Me NacnacTi(Cl)(η 2 -P-P t Bu 2 )] ( 2a ). In this run resonances of two diastereomers of t Bu 2 P–P(SiMe 3 )−P(SiMe 3 )−P t Bu 2 were detected, which points to the dimerization of t Bu 2 P–P(SiMe 3 ) groups. Additionally signals of t Bu 2 PH, t Bu 2 P–P(SiMe 3 )H and probably of t Bu 2 P−PH 2 were found.…”

Section: Results and Discussionmentioning

confidence: 69%

Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

2017

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β-Diketiminate complexes of Ti-containing phosphanylphosphido ligands [NacnacTi(Cl){η-P(SiMe)-PR}] (Nacnac = [Ar]NC(Me)CHC(Me)N[Ar]; Ar = 2,6-iPrCH) were prepared by reactions of [NacnacTiCl·THF] with lithium derivatives of diphosphanes RP-P(SiMe)Li (R = tBu, iPr) in toluene solutions. Surprisingly, reactions of [NacnacTiCl·THF] with RP-P(SiMe)Li in THF solutions led to Ti complexes containing phosphanylphosphinidene ligands [NacnacTi(Cl)(η-P-PtBu)] via an autoredox path involving a migration of a nitrene NAr from the Nacnac skeleton to the Ti centers. Solid-state structures of [NacnacTi(Cl){η-P(SiMe)-PtBu}] (1a) and [NacnacTi(Cl)(η-P-PtBu)] (two isomers 2a1, 2a2) together with [NacnacTi(Cl){η-P(SiMe)-PiPr}] (1b) and [NacnacTi(Cl)(η-P-PiPr)] (2b) were established by the single-crystal X-ray diffraction and display clearly side-on geometry of the (MeSi)P-PR and P-PR moieties in the solid state. Phosphanylphosphinidene complexes [NacnacTi(Cl)(η-P-PR)] indicate that the P NMR resonances of phosphinidene P atoms appear at a very low field in solution and in the solid state.

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Section: Results and Discussionmentioning

confidence: 69%

Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

2017

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“…The 1 H NMR signals for 2a , 2b , and 3b were established from 31 P‐ 1 H‐correlation spectra. t Bu 2 P–P(SiMe 3 )–P t Bu 2 was prepared in a one‐pot reaction 41 and lithiated according to literature procedures 42, t Bu 2 P–PLi–P(NEt 2 ) 2 was prepared according to literature procedures 43.…”

Section: Methodsmentioning

confidence: 99%

Reactions of Lithium Salts of Triphosphanes tBu₂P–PLi–PtBu₂ and tBu₂P–PLi–P(NEt₂)₂ with Metal Complexes [(R₃P)₂MCl₂] (M = Ni, Pd, Pt, R₃P = Et₃P, pTol₃P, Ph₂EtP, iPr₃P)

Wiśniewska¹,

Baranowska²,

Grubba³

et al. 2010

Zeitschrift anorg allge chemie

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tBu 2 P-PLi-PtBu 2 ·2THF reacts with [(R 3 P) 2 MCl 2 ] (M = Pt, Pd, Ni; R 3 P = Et 3 P, pTol 3 P, Ph 2 EtP, iPr 3 P) to yield isomers of [(1,2-η-tBu 2 P=P-PtBu 2 )M(PR 3 )Cl], in which the tBu 2 P-P-PtBu 2 ligand adopts the arrangement of a side-on bonded 1,1-di-tert-butyl-2-(di-tert-butyl-* Prof. Dr. J. Pikies E-Mail: jerzy.pikies@pg.gda.pl [a] 1549 phosphanyl)diphosphenium cation. tBu 2 P-PLi-P(NEt 2 ) 2 ·2THF reacts with [(R 3 P) 2 MCl 2 ] but does not form complexes with a tBu 2 P-P-P(NEt 2 ) 2 moiety, however, splitting of a P-P(NEt 2 ) 2 bond of the parent triphosphane takes place.

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“…Similarly with carbenes and nitrenes, [ 18 ] computational studies predict that only strong π‐donor substituents such as R 2 N‐ or R 2 P‐ could efficiently stabilize the singlet ground state. Fritz et al [ 19 ] and Breuers et al [ 20 ] generated a (phosphino)phosphinidene, which was unstable, and underwent dimerization and oligomerization. Liu et al synthesized a stable (phosphino)phosphinidene at room temperature in the presence of a bulky substituent.…”

Section: Introductionmentioning

confidence: 99%

A quest for substituent effects on novel diamino(phosphino)phosphinidenes using density functional theory method

Khorshidvand

Kassaee

2022

J of Physical Organic Chem

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Substituent effects on singlet (s) and triplet (t), symmetric acyclic (1X), cyclic‐saturated (2X), and cyclic‐unsaturated (3X) diamino(phosphino)phosphinidenes are investigated, at B3LYP/6‐311++G** level of theory (X = H, Me, t‐Bu, NH2, OH, Ph, CF3, and CN). All novel phosphinidenes scrutinized show singlet ground state, suggested by the conductor‐like polarizable continuum model (CPCM) on both gas‐phase and solvent‐phase optimized structures. Singlet–triplet energy gap (ΔES–T) increases in going from acyclic to cyclic‐saturated and cyclic‐unsaturated structures in gas phase. Band gap (ΔEH–L) decreases in going from cyclic‐saturated to cyclic‐unsaturated and to acyclic structures. Proton affinity (PA) decreases in going from acyclic to cyclic‐unsaturated and cyclic‐saturated structures in gas phase. Inverse pKa increases in both polar solvents (water and DMSO). Most our phosphinidenes appear as superacids in gas phase.

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Synthese und Eigenschaften teilsilylierter Tri‐ und Tetraphosphane. Reaktionen lithiierter Diphosphane mit Chlorphosphanen

Cited by 39 publications

References 15 publications

Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithium Salts of Triphosphanes tBu₂P–PLi–PtBu₂ and tBu₂P–PLi–P(NEt₂)₂ with Metal Complexes [(R₃P)₂MCl₂] (M = Ni, Pd, Pt, R₃P = Et₃P, pTol₃P, Ph₂EtP, iPr₃P)

A quest for substituent effects on novel diamino(phosphino)phosphinidenes using density functional theory method

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Synthese und Eigenschaften teilsilylierter Tri‐ und Tetraphosphane. Reaktionen lithiierter Diphosphane mit Chlorphosphanen

Cited by 39 publications

References 15 publications

Reactions of Lithiated Diphosphanes R2P–P(SiMe3)Li (R = tBu and iPr) with [MeNacnacTiCl2·THF] and [MeNacnacTiCl3]. Formation and Structure of TitaniumIII and TitaniumIV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithiated Diphosphanes R2P–P(SiMe3)Li (R = tBu and iPr) with [MeNacnacTiCl2·THF] and [MeNacnacTiCl3]. Formation and Structure of TitaniumIII and TitaniumIV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithium Salts of Triphosphanes tBu2P–PLi–PtBu2 and tBu2P–PLi–P(NEt2)2 with Metal Complexes [(R3P)2MCl2] (M = Ni, Pd, Pt, R3P = Et3P, pTol3P, Ph2EtP, iPr3P)

A quest for substituent effects on novel diamino(phosphino)phosphinidenes using density functional theory method

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Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithiated Diphosphanes R₂P–P(SiMe₃)Li (R = tBu and iPr) with [^MeNacnacTiCl₂·THF] and [^MeNacnacTiCl₃]. Formation and Structure of Titanium^III and Titanium^IV β-Diketiminato Complexes Bearing the Side-on Phosphanylphosphido and Phosphanylphosphinidene Functionalities

Reactions of Lithium Salts of Triphosphanes tBu₂P–PLi–PtBu₂ and tBu₂P–PLi–P(NEt₂)₂ with Metal Complexes [(R₃P)₂MCl₂] (M = Ni, Pd, Pt, R₃P = Et₃P, pTol₃P, Ph₂EtP, iPr₃P)