Phosphine Acetylenic Macrocycles and Cages: Synthesis and Reactivity

Weymiens, Wannes; Slootweg, J. Chris; Lammertsma, Koop

doi:10.1007/978-90-481-3817-3_2

Cited by 6 publications

(3 citation statements)

References 129 publications

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“…Calcd for C 33 H 39 BIN 6 O 2 PW (904.23 g mol −1 ): C 44.03 (calcd 43.83), H 4.50 (4.35), N 8.96 (9.29) %. 1 H NMR (CDCl 3 , 300 MHz, 300 K): δ = 13.66 (d, 3 J PH = 3.8 Hz, 1 H, CCH syn ), 7.47−7.29 (m, 6 H, Ph-H), 7.15 (m, 2 H, Ph-H), 6.90 (m, 2 H, Ph-H), 2.69 (s, 3 H, CCH 3 ), 2.54 (s, 3 H, CCH 3 ), 2.38 (s, 3 H, CCH 3 ), 2.35 (s, 3 H, CCH 3 ), 2.22 (s, 3 H, CCH 3 ), 1.78 (s, 3 H, CCH 3 ), 1.74 (s, 3 H, CCH 3 ), 1.55 (s, 3 H, CCH 3 ), 1.11 (s, 3 H, CCH 3 ) ppm. 13 C NMR (CDCl 3 , 75 MHz, 300 K): δ = 228.5 (d, 3 J CP = 3.2 Hz, WCO), 215.4 (d, 2 J CP = 4.0 Hz, WC syn ), 204.7 (d, 1 J CP = 88.3 Hz, WC anti ), 154.6, 152.5, 147.2, 143.4, 141.9, 140.5 (CCH 3 ), 135.9, 134.5 (C ipso ), 131.4− 127.3 (10 C, Ph), 113.5, 113.2, 112.8 (CCH 3 ), 18.7, 16.8, 13.5, 11.2, 10.9, 10.7, 8.3, 8.2, 8.2 (CCH 3 ) ppm.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Electron-rich donor-substituted alkynes with heteroatoms like N, P, O, or S in both α-positions are valuable ditopic ligands for polynuclear complexes showing a variety of bridging motifs with up to four metals . However, the majority of reported compounds exhibit structures, in which the unsaturated backbone is merely used as a linear spacer between two donating atoms. − If however all four potential donor atoms are involved, complexes with very short intermetallic distances are obtained. Investigations on the redox behavior of such polynuclear systems reveal the extent of electronic coupling of the side-on carbon-bonded metal with the donor chelate coordinated one.…”

Section: Introductionmentioning

confidence: 99%

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The Influence of Stepwise P-Oxidation on the Coordination and Redox Behavior of W–Bisphosalkyne Complex Ligands

2017

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The terminal phosphine groups at the tungsten bisphosphine alkyne complex [Tp*W(CO)(I)(η2-C,C′-Ph2PC2PPh2)] (2) {Tp* = hydridotris(3,4,5-trimethylpyrazolyl)borate} were selectively oxidized by common methods to form the alkyne complexes 2EE (E = O, S) with either two phosphine oxide or two phosphine sulfide substituents. The respective mono-oxidized analogues 2E (E = O, S) were obtained by subjecting the already oxidized intermediates [Tp*W(CO)(I)(η2-C,C′-Ph2P(E)C2H)] 1E (E = O, S) to a late-stage phosphine introduction at the complex template. These modulations of the peripheral alkyne moiety have a clear impact on the redox potential of the metal-based oxidation altering the W(II/III) potential by +0.1 V on average per oxidized phosphine. In contrast to the comparable redox behavior of 2O and 2S, the coordination behavior of these complex ligands differs substantially. XRD studies show that complex 2 and the sulfide 2S act either as a P,P’- or P,S-chelate ligand leading to the dinuclear complexes [(2)PdCl2], 3, and [(2S)PdCl2], 3S. In contrast, the corresponding PdCl2 complex of the monoxide 2O is connected by the free phosphine group and the W-bonded iodide as a μ2-bridging ligand leaving the phosphine oxide pending. A similar binding mode was found for the trinuclear gold complex [(2)2Au][PF6] (5-PF6). Furthermore, these findings explain the undesired outcome in the reaction of [Pd(NCMe)4][BF4]2 with two equivalents of 2, which resulted in the iodide abstraction product [(2)PdI2] (4).

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Section: ■ Conclusionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Influence of Stepwise P-Oxidation on the Coordination and Redox Behavior of W–Bisphosalkyne Complex Ligands

2017

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“…In the past, these phosphines were mainly used in coordination chemistry for the assembly of various mono- or bi-metallic complexes and clusters [ 3 ], by taking advantage of their diverse coordination modes to transition metals, via the phosphorus atom and/or the triple bond. It is noteworthy that the range of alkynylphosphines involved in those complexes and clusters is almost exclusively covered by diphenylphosphino-phenylacetylene and bis(diphenylphosphino)acetylene.…”

Section: Introductionmentioning

confidence: 99%

Stoichiometric and Catalytic Synthesis of Alkynylphosphines

et al. 2012

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Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.

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