Insertion Reactions of Nitriles into the P−C Bond of [(η1-C5Me5)P{W(CO)5}2]—A Novel Approach to Phosphorus-Containing Heterocycles

Schiffer, Michael; Scheer, Manfred

doi:10.1002/1521-3773(20010917)40:18<3413::aid-anie3413>3.0.co;2-1

Cited by 37 publications

(30 citation statements)

References 28 publications

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“…Both P–S bonds are of almost the same lengths. The other representative bond lengths and angles are in good agreement with the numerous data reported in the literature , , …”

Section: Resultssupporting

confidence: 90%

A Straightforward Synthesis of 1,2‐Azaphosphindoles

et al. 2017

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“…Both P–S bonds are of almost the same lengths. The other representative bond lengths and angles are in good agreement with the numerous data reported in the literature , , …”

Section: Resultssupporting

confidence: 90%

A Straightforward Synthesis of 1,2‐Azaphosphindoles

et al. 2017

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“…With the change of the coordination geometry also an elongation of the EÀW bonds occurs. [11] The newly formed PÀC and AsÀC bonds are 1.796(6) and 1.960(6) and hence in the normal range of single bonds.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Bridged Pentelidene Complexes with Isonitriles: A New Way to Pentel‐Containing Heterocycles

Seidl¹,

Schiffer²,

Bodensteiner³

et al. 2013

Chemistry A European J

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The reaction of [Cp*E{W(CO)5 }2 ] (E=P (1 a), As (1 b); Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) with isonitriles RNC (R=tBu, cyclohexyl (Cy), nBu) depends on the steric demand of the substituent at the isonitrile as well as on the stoichiometry of the starting materials. With tBuNC only the Lewis acid/base adducts [Cp*E{W(CO)5 }2 (CNtBu)] (E=P (2 a), As (2 b)) are formed. The use of Cy and n-butylisonitrile leads first to the formation of the Lewis acid/base adduct, but only at low temperatures. At ambient temperatures, a rearrangement occurs and bicyclo[3.2.0]heptane derivatives of the type [{C(Me)C(CH2 )C(Me)C(Me)C(Me)}C(NR)- E{W(CO)5 }2 ] (E=P, As; R=Cy, nBu) (3 a-Cy, 3 b-Cy, 3 a-nBu and 3 b-nBu) are obtained. The use of a further equivalent of isonitrile results in products revealing two new structural motifs, the four-membered ring derivatives [C(Cp*)N(R)C(NR)E{W(CO)5 }2 ] (4: E=P, As; R=Cy, nBu) and the bicyclic complexes [[{C(Me)C- (CH2 )C(Me)C(Me)C(Me)}C(NR)2 - E{W(CO)5 }2 ] (5: E=As; R=Cy). The reaction pathway depends on the substituent at the isonitrile. By treatment of 1 a with two equivalents of CyNC only a 2H-1,3-azaphosphet complex 4 a-Cy (E=P; R=Cy) is formed. Treatment of 1 b with two equivalents of CyNC exclusively leads to the complex 5 b-Cy (E=As; R=Cy). Treatment of 1 a with two equivalents of nBuNC results in a mixture of complexes, the 2H-1,3-azaphosphet 4 a-nBu (E=P; R=nBu) and the bicyclic complex 5 a-nBu (E=P; R=nBu). For the arsenidene complex 1 b a mixture of the 2H-1,3-azarsete complex 4 b-nBu (E=As; R=nBu) and the bicyclic complex 5 b-nBu (E=P, As; R=Cy, nBu) is obtained. Complex 4 b-nBu is the first example of a 2H-1,3-azarsete complex. All products have been characterized by using mass spectrometry, NMR spectroscopy, and X-ray diffraction analysis.

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“…NC t Bu, with no βH atoms, did not react with the phosphinidene even in refluxing toluene for 2 days. However, benzonitrile reacted at ambient temperature to give a 3,4-benzo-1H-1,2-azaphosphole derivative 148a, which proves that after insertion of the nitrile into the PC bond, an additional CH bond activation occurs [102].…”

Section: Reactions With Molecules Containing Cn Multiple Bondsmentioning

confidence: 91%

“…The reactivity of the ditungsten complex 5 towards molecules containing multiple CN bonds such as nitriles [57,102], isocyanides [103], carbodiimides [104] and carboimidophosphenes [105] has been examined in detail (Schemes 72 and 73). Reaction with acetonitrile proceeded at 293 K to give a 1,2-dihydro-1,3,2-diazaphosphinine derivative 147a following from double NCMe insertion into the PC bond of the phosphinidene ligand, with CC bond formation and subsequent migration of βH atoms of one acetonitrile to the N atoms.…”

Section: Reactions With Molecules Containing Cn Multiple Bondsmentioning

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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Insertion Reactions of Nitriles into the P−C Bond of [(η1-C5Me5)P{W(CO)5}2]—A Novel Approach to Phosphorus-Containing Heterocycles

Cited by 37 publications

References 28 publications

A Straightforward Synthesis of 1,2‐Azaphosphindoles

A Straightforward Synthesis of 1,2‐Azaphosphindoles

Reactivity of Bridged Pentelidene Complexes with Isonitriles: A New Way to Pentel‐Containing Heterocycles

Phosphinidene-bridged binuclear complexes

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