Synthesis, X-ray Crystal Structures and Reactivity Towards Alkynes of Gold(I)–Phosphinine Complexes

Mézailles, Nicolas; Ricard, Louis; Mathey, François; Floch, Pascal Le

doi:10.1002/(sici)1099-0682(199912)1999:12<2233::aid-ejic2233>3.0.co;2-2

Cited by 39 publications

(26 citation statements)

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“…In order to demonstrate the efficacy of phosphinines 1a – c and 2a – c as ligands, we prepared gold complexes from the free ligands and an equimolar amount of AuCl(tht) (tht = tetrahydrothiophene) in CH 2 Cl 2 or thf, respectively. Gold(I) was chosen since phosphinines form stable complexes with this metal that are distinguished by a 1:1 metal‐to‐ligand ratio and are not supported by additional ligands 10 and thus possibly minimise the chance of decomposition during subsequent immobilisation. Model complexes 3a / b and 4a were isolated as pale yellow solids in 90–95 % yield after precipitation with hexane and identified by spectroscopic data and a single‐crystal X‐ray diffraction study of 4a .…”

Section: Resultsmentioning

confidence: 99%

On the Surface Reactivity of Functionalized Phosphinines on Inorganic Supports

Mallissery

Nieger

Gudat

2010

Zeitschrift anorg allge chemie

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Phosphinines with pendant phenol or catechol functionalities and their gold(I) complexes were synthesised and characterised by spectroscopic data and in one case by a single-crystal X-ray diffraction study. Reactions of ligands or complexes with TiO 2 or chloropropyl modified hexagonal mesoporous silica were then studied with the aim to immobilise ligands or complexes on the carrier by covalent tethering. 31 P MAS NMR studies revealed that immobilisation on TiO 2 www.zaac.wiley-vch.de 1359 3a: from 1a (100 mg, 0.28 mmol) and AuCl(tht) (90 mg, 0.28 mmol). Yield: 150 mg (91 %); m.p. 202°C. C 23 H 17 O 2 P 1 Cl 1 Au 1 (588.78): calcd. C 46.92, H 2.91; found C 47.84, H 3.53. 31 P{ 1 H} NMR (CD 2 Cl 2 ): δ = 152.40. 1 H NMR (CD 2 Cl 2 ): δ = 6.88 (dd, 3 J HH = 0.8, 4 J HP = 8.2 Hz, 1 H), 7.18 (dt, 4 J HH = 2.2, 3 J HP = 8.1 Hz, 1 H), 7.28-7.35 (m, 1 H), 7.41-7.57 (m, 6 H), 7.77-7.88 (m, 4 H), 8.44 (dd, 4 J HH = 1.6, 3 J HP = 22.4 Hz, 1 H, H at C3/C5), 8.52 (dd, 4 J HH = 1.6, 3 J HP = 22.4 Hz, 1 H, H at C3/C5).

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Section: Resultsmentioning

confidence: 99%

On the Surface Reactivity of Functionalized Phosphinines on Inorganic Supports

Mallissery

Nieger

Gudat

2010

Zeitschrift anorg allge chemie

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“…The reactivities as dienes or dienophiles are sharply enhanced upon P-complexation [150][151][152][153] or sulfurization [122,154,155]. Some examples are depicted in Schemes 23.57-23.59.…”

Section: Cycloaddition Reactionsmentioning

confidence: 99%

Phosphorus Heterocycles

Mathey

2011

Modern Heterocyclic Chemistry

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Figure 23.1 The three isomers of the phosphole system (A-C) and the phospholide ion (D).2072j 23 Phosphorus Heterocycles shown with 1-alcoxyphospholes, which are relatively flat with a negligible delocalization [12]. Contrary to phospholes, the structure of phospholide ions reflects their high aromaticity. For example, the planar 2,3,4,5-tetramethylphospholide with Li(TMEDA) þ as the counterion displays the following parameters [13]: P-C, 1.715 A ; C¼C, 1.396 A ; CÀC, 1.424 A ;

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“…Indeed, they synthesized a series of homoleptic complexes of the parent phosphinine C 5 H 5 P, (5). Finally, homoleptic 1 complexes of gold(I) were reported [52]. 5).…”

Section: Coordinationmentioning

confidence: 99%

“…In the same report, the ruthenium complex (52) was employed in the transfer hydrogenation of ketones with modest TON ranging from 82 to 200. In the same report, the ruthenium complex (52) was employed in the transfer hydrogenation of ketones with modest TON ranging from 82 to 200.…”

Section: Current Areas Of Researchmentioning

confidence: 99%

The Chemistry of Phosphinines: Syntheses, Coordination Chemistry and Catalysis

Mézailles¹,

Floch

2006

COC

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This review deals with the chemistry of phosphinines. As many reviews are available on the syntheses of these derivatives, only the most versatile methods are presented, or the ones giving access to the phosphinines that have been particularly studied. Then, recent results obtained in the coordination chemistry of phosphinines are summarized with an emphasis on their analogy with CO ligands. Indeed, the first studies proved these ligands to be well adapted for the stabilization of electron rich metal centers. Shortly after, highly reduced complexes have been obtained through the reaction of reduced 2,2'-biphosphinine dianions with transition metal fragments. Theoretical calculations were performed to establish the oxidation state of the metal in these complexes. On the other hand, the various coordination studies have pointed out that phosphinines become sensitive toward nucleophiles once they are bound to (even slightly) oxidized metal centers. This sensitivity precluded their use in most catalytic processes, but the cases in which they could be used efficiently are presented in this review. Two ways to circumvent this drawback were developed lately. The first method relies on the use of the high electrophilicity of the phosphorus atom of the phosphinine moiety. The ring is readily transformed into phosphacyclohexadienyl anions, which exhibit surprising coordination chemistry and promising behavior in catalysis. Results in this domain are presented. The second method is based on the involvement of the ring, as phosphadiene, into [4+2] Diels Alder type cycloadditions leading to phosphabarrelene derivatives. These ligands also show promising results in catalytic processes. Finally, phosphinines have been used successfully to stabilize gold nanoparticles, which opens a whole new field of applications for these ligands. P P _ 88% 100% _ The Chemistry of Phosphinines

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Synthesis, X-ray Crystal Structures and Reactivity Towards Alkynes of Gold(I)–Phosphinine Complexes

Cited by 39 publications

References 50 publications

On the Surface Reactivity of Functionalized Phosphinines on Inorganic Supports

On the Surface Reactivity of Functionalized Phosphinines on Inorganic Supports

Phosphorus Heterocycles

The Chemistry of Phosphinines: Syntheses, Coordination Chemistry and Catalysis

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