Deoxygenation of chalcogen oxides EO<sub>2</sub> (E = S, Se) with phospha-Wittig reagents

Dankert, Fabian; Gupta, Priyanka; Wellnitz, Tim; Baumann, Wolfgang; Hering‐Junghans, Christian

doi:10.1039/d2dt03703c

Cited by 3 publications

(3 citation statements)

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“…Liu and co-workers have recently introduced the class of AuPhos ligands, with the general formula LAu−PR 2 (L = NHC, R = H, Ad, Ph), which could further yield (LAu) 2 PiPr (Au 2 Phos), of which the Rh(acac)CO complex was prepared and showed that Au 2 Phos is a very electron-rich ligand. [38] Compared to the free ligand 1 and Rh complex 4, the P−C NHC distances in 7 (1.836 (7) The short Au•••Au distance (2.9838(4) Å) indicates the presence of an aurophilic interaction through the 1•Rh metallacycle, [39] which is in the same range as those measured in the complex [Me ( Dip TerPO 2 )OPMe 3 [41] 1.4641 (19), 1.4721(17) Å; (PhPO 2 )dmap [42] 1.4752(17), 1.4742( 14)).…”

Section: Resultsmentioning

confidence: 89%

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Siewert

Lombardi

Janssen

et al. 2023

Preprint

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N-heterocyclic carbene-phosphinidene adducts (NHPs) are an emerging class of ligands with proven binding ability for main group and transition elements. They can be considered as inversely polarized phosphaalkenes with electron-rich P atoms possessing two lone pairs of electrons, which render them interesting platforms for the formation of multi-metallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHP)s, starting from alkylidene-bridged bis(NHC)s ((IMe)}2CnH2n; n = 1,3) and a triphosphirane (cyclo-P3Dip3) (Dip = 2,6-iPr2C6H3) as phosphinidene transfer reagents. The coordination chemistry of [{DipP(IMe)}2CH2], 1, was studied in detail, and the complexes [1∙FeBr2] and [1∙Rh(cod)]Cl were prepared, showing that the ligand has a flexible bite-angle ranging between 86-106°. [1∙Rh(cod)]Cl was converted into the corresponding dicarbonyl complex [1∙Rh(CO)2]Cl, with an average value for the CO stretching frequency of 2029 cm−1, which indicates a strongly donating ligand, when compared to related bis(NHC) rhodium complexes. The binding ability of the remaining two phosphorus lone pairs was demonstrated via addition of AuCl(SMe2), which generated the hetero-trimetallic complex [1∙(AuCl)2∙Rh(cod)]Cl. Moreover, [1∙Rh(cod)]X (X− = Cl, B(3,5-CF3-C6H3)4) were tested in the catalytic hydrogenation of the α,β-unsaturated esters methyl-Z-α-acetamidocinnamate (MAC) and dimethyl itaconate (ItMe2), revealing that the chloride complex was inactive, while the BArF-complex demonstrated moderate activity, lower than that of analogous complexes incorporating classical diphosphines such as DiPAMP. In addition, [1∙Rh(cod)]Cl was shown to be moderately air- and moisture stable, slowly decomposing to the corresponding NHC-stabilized bisdioxophosphorane, which was independently synthesized by treating the free ligand with dry O2.

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Section: Resultsmentioning

confidence: 89%

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Siewert

Lombardi

Janssen

et al. 2023

Preprint

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“…(PhPO 2 )IMe 4 1.4902(10), 1.4855(11) Å) and other Lewis base stabilized dioxophosphoranes (cf. ( Dip TerPO 2 )OPMe 3 1.4641(19), 1.4721(17) Å; (PhPO 2 )dmap 1.4752(17), 1.4742(14)). Additionally, the P–C NHC distances (1.8715(19), 1.8660(19) Å) increase significantly upon oxidation, compared to those observed in the free ligand 1 (cf.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Ligand Properties of Chelating Bis(N-heterocyclic carbene)-Stabilized Bis(phosphinidenes)

Siewert,

Puerta Lombardi,

Jannsen

et al. 2023

Inorg. Chem.

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NHC−phosphinidene (NHCP) adducts are an emerging class of ligands with proven binding ability for main group and transition metal elements. They possess electron-rich P atoms with two lone pairs (LPs) of electrons, making them interesting platforms for the formation of multimetallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHCP)s, starting from alkylidene-bridged bis(NHC)s ((IMe) 2 C n H 2n ; n = 1,3) and triphosphirane (PDip) 3 (Dip = 2,6-iPr 2 C 6 H 3 ) as phosphinidene transfer reagent. The coordination chemistry of [{DipP(IMe)} 2 CH 2 ], 1, was studied in detail, and complexes [1• FeBr 2 ] and [1•Rh(cod)]Cl were prepared, showing that the ligand has a flexible bite angle. The dicarbonyl complex [1•Rh(CO) 2 ]Cl, with an average value for the CO stretching frequency of 2029 cm −1 , indicates a strongly donating ligand when compared to related complexes. The binding ability of the remaining two phosphorus LPs was demonstrated with AuCl(SMe 2 ), giving the heterotrimetallic complex [1•(AuCl) 2 •Rh(cod)]Cl. Moreover, [1•Rh(cod)]X (X − = Cl, B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 ) was tested in the catalytic hydrogenation of methyl-Z-α-acetamidocinnamate (MAC) and dimethyl itaconate (ItMe 2 ), revealing that the chloride complex was inactive, while the BAr F complex demonstrated moderate activity. Additionally, [1•Rh(cod)]Cl was shown to be moderately air-and moisture-stable, slowly decomposing to the corresponding NHC-stabilized bis-dioxophosphorane, which was independently synthesized by treating the free ligand with dry O 2 .

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“…We recognized that the use of select phosphorus reagents in initial FLP addition reactions could provide a new P-C bond and yet retain the capacity for further reaction. To this end, we noted the innovative work from the groups of Cummins, 22,23 Protasiewicz [24][25][26][27] and Hering-Junghans [28][29][30][31][32][33] that have described the chemistry of phosphinidene precursors. Herein, we first demonstrate that these species do participate in FLPalkyne addition reactions.…”

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confidence: 99%

Reactive FLP–alkyne addition products: a route to anionic and zwitterionic phosphines

Kim

Stephan

2023

Dalton Trans.

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Deoxygenation of chalcogen oxides EO₂ (E = S, Se) with phospha-Wittig reagents

Abstract: In here we present the deoxygenation of the chalcogen oxides EO2 (E = S, Se) with R–P(PMe3), so-called phospha-Wittig reagents. The reaction of DABSO (DABCO⋅2SO2) with R–P(PMe3) (R = Mes*,...

Cited by 3 publications

References 86 publications

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Synthesis and Ligand Properties of Chelating Bis(N-heterocyclic carbene)-Stabilized Bis(phosphinidenes)

Reactive FLP–alkyne addition products: a route to anionic and zwitterionic phosphines

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Deoxygenation of chalcogen oxides EO2 (E = S, Se) with phospha-Wittig reagents

Abstract: In here we present the deoxygenation of the chalcogen oxides EO2 (E = S, Se) with R–P(PMe3), so-called phospha-Wittig reagents. The reaction of DABSO (DABCO⋅2SO2) with R–P(PMe3) (R = Mes*,...

Cited by 3 publications

References 86 publications

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Synthesis and ligand properties of chelating bis(N-heterocyclic carbene)-stabilized bis(phosphinidenes)

Synthesis and Ligand Properties of Chelating Bis(N-heterocyclic carbene)-Stabilized Bis(phosphinidenes)

Reactive FLP–alkyne addition products: a route to anionic and zwitterionic phosphines

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Deoxygenation of chalcogen oxides EO₂ (E = S, Se) with phospha-Wittig reagents