Reactivity of allylphosphines with iridium complexes: Diallylphosphines as new bidentate ligands

Ocando-Mavárez, Edgar; Rosales, Merlín; Silva, Ninoska

doi:10.1002/(sici)1098-1071(1998)9:2<253::aid-hc21>3.0.co;2-p

Cited by 10 publications

(4 citation statements)

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“…Compounds with similar motifs have been reported [27,28] . Notwithstanding, this reactivity does differ from related iridium compounds bearing monophosphine allyl ligands, where C−H cyclometallation was witnessed [12,29] …”

Section: Reactions With Ir‐μ‐och3 Precursorsmentioning

confidence: 61%

“…[27,28] Notwithstanding, this reactivity does differ from related iridium compounds bearing monophosphine allyl ligands, where CÀ H cyclometallation was witnessed. [12,29] Notably, compound 7 is C 1 -symmetric, causing its 1 H NMR spectrum between 6.2 � δ H � 4.4 ppm and 3 � δ H � 0.9 ppm to appear convoluted (Scheme 4, Figure 2, and Supporting Information). By 1 H NMR spectroscopy, four multiplets at δ H = 6.07, 5.95, 5.82 and 5.…”

Section: Reactions With Ir-μ-och 3 Precursorsmentioning

confidence: 99%

“…[11] Diphosphine ligand systems were chosen due to an ease in manipulation of both primary and secondary coordination sphere; iridium-phosphorus bonds are also known to be additionally robust and allow for facile probing using 31 P NMR spectroscopy. [12][13][14] Moreover, it has been shown that diphosphine ligands are viable candidates for iridium-catalysed arene and heteroarene borylation. [15][16][17] The ligand system of interest, 1,2-bis(di(3-dicyclohexylboraneyl)propylphosphino)ethane (P 2 B Cy 4 ) was previously reported by members of our team in 2020, and was shown to coordinate Lewis basic molecules, such as 4-N,N,-dimethylaminopyridine (DMAP) via its Lewis acidic secondary coordination sphere; this scaffold has also been used to assist in small molecule activation and transmetalation reactions using gold(I) pyridyl compounds.…”

Section: Introductionmentioning

confidence: 99%

“…We anticipated that this could be tested by first synthesizing an allyl‐substituted phosphine‐ligated iridium complex, which could then be hydroborated to create a phosphinoboranyl iridium complex [11] . Diphosphine ligand systems were chosen due to an ease in manipulation of both primary and secondary coordination sphere; iridium‐phosphorus bonds are also known to be additionally robust and allow for facile probing using 31 P NMR spectroscopy [12–14] . Moreover, it has been shown that diphosphine ligands are viable candidates for iridium‐catalysed arene and heteroarene borylation [15–17] .…”

Section: Introductionmentioning

confidence: 99%

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Iridium Diphosphine Complexes Featuring Pendant Lewis Acids: Efforts toward Selective Heteroarene Borylation

2022

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The selective forging of carbon‐boron bonds via C−H borylation stands as a central means to access fine chemical precursors. Notwithstanding, achieving selectivity in this reaction is difficult, calling for the design of molecular catalysts that offer a vector for mechanistic control. This report aims to achieve such through the strategic placement of Lewis acids in the ligand periphery, permitting engagement with a substrate through non‐covalent Lewis acid/base interactions. Various diphosphine iridium(I/III) complexes having 1,2‐bis(di‐n‐propylphosphino)ethane) (dnppe), tetrakisallylphosphinoethane (tape) and 1,2‐bis(di(3‐dicyclohexylboranyl)propylphosphino)ethane (P2BCy4) ligands were prepared. The P2BCy4 ligand scaffold boasts four Lewis acidic boron groups in its secondary coordination sphere, which are shown to engage with N‐heterocycles, tape is the precursor to P2BCy4, and dnppe is a saturated n‐propyl analogue devoid of boron functionality. Select combinations of such iridium salts/diphosphine ligands were assayed in the catalytic borylation of 2‐methylpyridine using B2Pin2 (Pin=pinacol).

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Section: Reactions With Ir‐μ‐och3 Precursorsmentioning

confidence: 61%