Umpolung of Electrophilic Terminal Phosphinidene Complexes by Interaction with Nucleophilic Carbenes

Huy, Ngoc Hoa Tran; Donnadieu, Bruno; Bertrand, Guy; Mathey, François

doi:10.1002/asia.200900177

Cited by 27 publications

(14 citation statements)

References 22 publications

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“…[22g, 34] It might also be interesting to note that metal complexes containing carbene-phosphinidene adducts of type 1 and related species can be regarded as carbene-stabilized phosphinidene-metal complexes, [10a, 30] and indeed, trapping of the phosphinidene complex [(PhP)W(CO) 5 ] by addition of a stable diaminocyclopropenylidene has been reported. [35] Likewise, complexes such as 7 and 8 might be formally regarded as NHC-stabilized terminal phosphinidyne (or phosphido) metal complexes [36] of the type NHC!PML n , and the possibility of interconversion between these species will be further explored.…”

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N‐Heterocyclic Carbene–Phosphinidyne Transition Metal Complexes

et al. 2014

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The N-heterocyclic carbene-phosphinidene adduct IPrPSiMe3 is introduced as a synthon for the preparation of terminal carbene-phosphinidyne transition metal complexes of the type [(IPrP)MLn ] (MLn =(η(6) -p-cymene)RuCl) and (η(5) -C5 Me5 )RhCl). Their spectroscopic and structural characteristics, namely low-field (31) P NMR chemical shifts and short metal-phosphorus bonds, show their similarity with arylphosphinidene complexes. The formally mononegative IPrP ligand is also capable of bridging two or three metal atoms as demonstrated by the preparation of bi- and trimetallic RuAu, RhAu, Rh2 , and Rh2 Au complexes.

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N‐Heterocyclic Carbene–Phosphinidyne Transition Metal Complexes

et al. 2014

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“…A related tungsten phosphinidene complex containing a donor bis(amino)cyclopropylidene moiety has been recently reported by the Bertrand group. 41 We have recently reported that the reactions of bimetallic μ-phosphinidene complexes [Mn 2 (CO) 8 {μ-P(N i Pr 2 )}] and [Co 2 (CO) 4 (μ-dppm){μ-P-(N i Pr 2 )}]a fford similar abnormal NCN carbene adducts and that the migration of the ylidene moiety appears to be induced by steric interactions between bulky di-R-imidazolylidene R groups and either the metal-bound ligands or the N i Pr 2 group bound to phosphorus. 42 We were also interested in the interaction of 3a with other types of reagents that are typically used to introduce carbene fragments into molecules.…”

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Synthesis and Structural Characterization of the First Thermally Stable, Neutral, and Electrophilic Phosphinidene Complexes of Vanadium

et al. 2011

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The first thermally stable, neutral, electrophilic phosphinidene complexes of vanadium, [CpV(CO)3{η1-P(NR2)}] (R = i Pr (3a), Cy (3b)), have been prepared by the reaction of [Na]2[CpV(CO)3] with Cl2PNR2. The molecules 3a and 3b have been characterized by microanalysis, IR, and 1H and 31P{1H} NMR spectroscopy, and for 3a also by single-crystal X-ray diffraction. The structure of 3a exhibits a piano stool geometry closely related to that of CpV(CO)4 with an η1-phosphinidene ligand replacing CO in one of the basal coordination sites of the vanadium atom (V(1)−P(1) = 2.300(2) Å). The reactivity of 3a toward a variety of unsaturated substrates: PhCCPh, di- t Bu-imidazol-2-ydene, PhN3, and Ph2CNN has been examined to probe the electrophilic (or nucleophilic) character of the low-coordinate P(I) site. In all cases reactions occur exclusively at the phosphinidene phosphorus atom, without CO displacement, affording examples of P-coordinated phosphirene [CpV(CO)3{P(N i Pr2)CPhCPh}] (7), abnormal NCN carbene adduct [CpV(CO)3{P(N i Pr2)-4-cyclo-C3H2-1,3-(N t Bu)2)}] (8), diazaphosphaimine [CpV(CO)3{P(N i Pr2)N−NCPh2}] (12), and P-coordinated phosphaimine [CpV(CO)3{P(N i Pr2)NPh}] (14) complexes. The η1-phosphaimine complexes 12 and 14 lose carbon monoxide to yield derivatives [CpV(CO)2{P(N i Pr2)N−NCPh2}] (9) and [CpV(CO)2{P(N i Pr2)NPh}] (15), which contain η2-(P,N)-coordinated phosphaimine ligands. An η3-(P,N,N)-bound phosphaimine ligand is present in an isomer of 9, namely, [CpV(CO)2{P(N i Pr2)N−NCPh2}], 13. Complexes 3a, 7, 8, 9, 14, and 15 have been characterized by X-ray crystallography.

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“…[10] To put our design concept into practice, we considered 1,2-bis(diisopropylamino)cyclopropenyl-3-ylidene as an internal carbene ligand that fulfils the necessary electronic requirements. [11] The preparation of cyclopropenylylidenestabilized phosphenium cations 2-7 was achieved in good to excellent yields after direct condensation of the readily available chlorocyclopropenium salt 1 [12] with a range of secondary phosphines and subsequent anion exchange. This synthetic strategy allowed the preparation of the desired salts on a multigram scale as white, air-stable solids (see Scheme 2 and the Supporting Information).…”

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“…Hydrogen atoms and the BF 4 anion are omitted for clarity; ellipsoids are set at 50 % probability. [16] (12)(13)(14)(15). The values for commonly used phosphorus ligands are also included for comparison.…”

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confidence: 99%