Stepwise Expansion of a Cp* Ring at Pentelidene Complexes and Stereoselective Formation of Triphosphines

Scheer, Manfred; Kuntz, Christian; Stubenhofer, Markus; Zabel, Manfred; Timoshkin, Alexey Y.

doi:10.1002/anie.200904827

Cited by 44 publications

(16 citation statements)

References 56 publications

(29 reference statements)

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“…In contrast, reaction with PH 2 t Bu proceeded at 363 K through elimination of HCp* to give a novel 1,2,3-trihydrotriphosphine 131a stabilised by two W(CO) 5 fragments [97].…”

Section: Scheme 64mentioning

confidence: 99%

Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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This article contains a comprehensive review of the work carried out within the last three decades on the synthesis, structural studies and reactivity of the binuclear complexes of transition and lanthanide elements bearing bridging phosphinidene (PR) ligands. The latter are grouped into three different classes according to their geometry and electronic distribution: pyramidal, symmetric planar trigonal and asymmetric planar trigonal. Different reactivity patterns can be then outlined for each of these classes of metal complexes, which differ in many ways from those characterizing the extensively studied chemical behaviour of mononuclear phosphinidene complexes.

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“…In contrast, reaction with PH 2 t Bu proceeded at 363 K through elimination of HCp* to give a novel 1,2,3-trihydrotriphosphine 131a stabilised by two W(CO) 5 fragments [97].…”

Section: Scheme 64mentioning

confidence: 99%

Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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“…To comparet he reactivity of benzonitrile and aniline with 1,t he phosphinidene complex 1 was reactedwith three different isomers of aminobenzonitrile (2-, 3-, and 4-aminobenzonitrile). [9][10][11] Chem. Compounds 5, 6a, 6b,a nd 7,w hich are derivativeso f1 ,2-dihydro-1,3,2-diazaphosphinine or benzo-2H-1,2-azaphospholes, were, as well as all other products, characterizedb ym ass spectrometry,N MR and IR spectroscopy,a nd X-ray structure analysis.…”

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confidence: 99%

“…Although terminally coordinated phosphinidene complexes( L n M=PR) are broadly investigated, [3] the reactivity of bridging phosphinidene complexes ([{L n M} 2À m-PR]) is less explored. [9][10][11] Chem. We investigated the reactivity of the Cp*-substituted m-phosphinidene complex [Cp*P{W(CO) 5 } 2 ] (1), whichw as first synthesized by Jutzi and Kross.…”

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confidence: 99%

Insight into the Reaction of a Dinuclear Phosphinidene Complex with Nitriles

Seidl

Weinzierl

Timoshkin

et al. 2016

Chemistry A European J

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The phosphinidene complex [Cp*P{W(CO)5}2] (1; Cp*=C5 Me5 ) reacted with malononitrile to give the 1,2-dihydro-1,3,2-diazaphosphinine derivative 2. The reaction of 1 with 1,4-benzodinitrile gave [1,4-{{W(CO)5}2 P-N=C(Cp*)}2 (C6 H4)] (3), the first example of a cumulene-like aminophosphinidene complex. The reaction of 1 with aniline gave the aminophosphinidene complex [(Ph)N(H)P{W(CO)5}2] (4). To compare the reactivity of benzonitrile and aniline with 1, the phosphinidene complex 1 was reacted with three different isomers of aminobenzonitrile (2-, 3-, and 4-aminobenzonitrile). These reactions gave an insight into the reaction pathway of 1 with benzonitrile derivatives. Compounds 5, 6 a, 6 b, and 7, which are derivatives of 1,2-dihydro-1,3,2-diazaphosphinine or benzo-2H-1,2-azaphospholes, were, as well as all other products, characterized by mass spectrometry, NMR and IR spectroscopy, and X-ray structure analysis.

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“…The formation of adducts was observed in some reactions of mphosphinidene complexes with Lewis bases, [10,20] but they could be isolated in only a few cases. First, the nucleophilic attack of the lone-pair of one nitrogen atom of the carbodii-mide at the Group 15 atom occurs to form adduct I.…”

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Reaction of Tungsten–Phosphinidene and –Arsinidene Complexes with Carbodiimides and Alkyl Azides: A Straightforward Way to Four‐Membered Heterocycles

et al. 2015

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The reaction of the phosphinidene and arsinidene complexes [Cp*E{W(CO)5 }2 ] (E=P (1 a), As (1 b); Cp*=C5 Me5 ) with carbodiimides leads to the new four-membered heterocycles of the type [Cp*C(NR)2 E{W(CO)5 }2 ] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). The reaction of phosphinidene complex 1 a with alkyl azides yields the triazaphosphete derivatives [Cp*P{W(CO)5 }N(R)NN{W(CO)5 }] (R=Hex, Cy) (4). These unprecedented N3 P four-membered triazaphosphete complexes can be regarded as stabilized intermediates of the Staudinger reaction, which have not been previously isolated. All of the isolated products were characterized by NMR, IR spectroscopy, mass spectrometry, and by single-crystal X-ray diffraction analysis.

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Stepwise Expansion of a Cp* Ring at Pentelidene Complexes and Stereoselective Formation of Triphosphines

Cited by 44 publications

References 56 publications

Phosphinidene-bridged binuclear complexes

Phosphinidene-bridged binuclear complexes

Insight into the Reaction of a Dinuclear Phosphinidene Complex with Nitriles

Reaction of Tungsten–Phosphinidene and –Arsinidene Complexes with Carbodiimides and Alkyl Azides: A Straightforward Way to Four‐Membered Heterocycles

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