Differences in the η1-ligating properties of 2,4,6-tritertiarybutyl-phosphabenzene, and 2,4,6-tritertiarybutyl-1,3,5-triphosphabenzene,

Clendenning, Scott B.; Hitchcock, Peter B.; Lawless, Gerard A.; Nixon, John F.; Tate, Christopher W.

doi:10.1016/j.jorganchem.2009.12.005

Cited by 18 publications

(9 citation statements)

References 17 publications

(21 reference statements)

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“…Thus, a planar geometry is found at the P atom with a small C‐P‐C angle (105°) and indistinguishable C−C distances within the ring (av 139 pm) consistent with a delocalized aromatic state. The Au−P distance (248 pm) is, however, appreciably longer than those found in linear gold(I) complexes of various substituted monodentate λ 3 ‐phosphinine ligands: ClAu(PC 5 H 2 t Bu 3 ‐2,4,6) (221.9(2) pm), ClAu(PC 5 H 2 Ph 2 ‐2,6‐Me−4) (av 220.62(7) pm), ClAu(PC 5 H 2 R 2 ‐2,6‐Ph‐4) (223.4(3) pm for R=Me; ca. 222 pm for R=Ph), ClAu(PC 5 H 2 R‐2‐Ph 2 ‐4,6) (av 220.8(1) pm; R=C 6 H 3 (OMe) 2 ‐3,4), ClAu{PC 5 HR‐2‐Me‐3‐Ph 2 ‐4,6} (220.40(7) pm; R=C 6 H 3 Me 2 ‐2,3), ClAu{PC 5 H 3 (SiMe 3 ) 2 ‐2,6} (221.1(2) pm), and [Au{PC 5 H 3 (SiMe 2 R) 2 ‐2,6} 2 ][GaCl 4 ] (av 228.2(4) pm for R=Me; av 226.3(2) pm for R=CCPh) .…”

Section: Resultsmentioning

confidence: 99%

“…Intermediates tabilization is attained with py (4: D e = 169 kJ mol À1 )a nd tBuNC (2: D e = 178 kJ mol À1 ). The AuÀPd istance (248 pm) is, however,a ppreciably longer than those found in linear gold(I) complexeso fv ariouss ubstituted monodentate l 3 -phosphinine ligands: ClAu(PC 5 H 2 tBu 3 -2,4,6) (221.9(2)pm), [59] ClAu(PC 5 H 2 Ph 2 -2,6-MeÀ4) (av 220.62(7)pm), [60] ClAu(PC 5 H 2 R 2 -2,6-Ph-4) (223.4(3) pm for R = Me;c a. In the (CF 3 ) 3 Au(SiNtBu) complex ( Figure S6 in the Supporting Information), the silylatedl igand is coordinated in a highly asymmetric way,c learly slipped towards the Na tom.…”

Section: Ligand Affinity Of the (Cf 3 ) 3 Au Fragmentmentioning

confidence: 90%

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(CF₃)₃Au as a Highly Acidic Organogold(III) Fragment

Pérez‐Bitrián

Baya

Casas

et al. 2017

Chemistry A European J

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The Lewis acidity of perfluorinated trimethylgold (CF ) Au was assessed by theoretical and experimental methods. It was found that the (CF ) Au unit is much more acidic than its nonfluorinated analogue (CH ) Au, and probably sets the upper limit of the acidity scale for neutral organogold(III) species R Au. The significant acidity increase on fluorination is in line with the CF group being more electron-withdrawing than CH . The solvate (CF ) Au⋅OEt (1) is presented as a convenient synthon of the unsaturated, 14-electron species (CF ) Au. Thus, the weakly coordinated ether molecule in 1 is readily replaced by a variety of neutral ligands (L) to afford a wide range of (CF ) Au⋅L compounds, which were isolated and characterized. Most of these mononuclear compounds exhibit marked thermal stability. This enhanced stabilization can be rationalized in terms of substantially stronger [Au]-L interactions with the (CF ) Au unit. An affinity scale of this single-site, highly acidic organogold(III) fragment was calculated by DFT methods and experimentally mapped for various neutral monodentate ligands. The high-energy profile calculated for the fluorotropic [Au]-CF ⇌F-[Au]←CF process makes this potential decomposition path unfavorable and adds to the general stabilization of the fragment.

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Section: Resultsmentioning

confidence: 99%

Section: Ligand Affinity Of the (Cf 3 ) 3 Au Fragmentmentioning

confidence: 90%

(CF₃)₃Au as a Highly Acidic Organogold(III) Fragment

Pérez‐Bitrián

Baya

Casas

et al. 2017

Chemistry A European J

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“…Pd-phosphinine complexes are relatively rare. Monodentate complexes of 2,4,6-tri-tert-butylphosphinine with Pd(II), Pt(II) and Au(I) have been reported [59] along with chelating complexes of 2-pyridyl-4,6-diphenylphosphinine to PdCl 2 , which was poorly soluble and featured a 31 P NMR chemical shift of 159 ppm [60], as well as [PdCl 2 {2-(PPh 2 O)PC 5 H 4 }], which gave a doublet at 165.9 ppm for the phosphinine P atom [61]. Other Pd complexes usually feature P-substituted phosphahexadienyl anions [38][39][40]45,62].…”

Section: Resultsmentioning

confidence: 99%

Reactivity Studies of Phosphinines: The Selenation of Diphenyl-Phosphine Substituents and Formation of a Chelating Bis(Phosphinine) Palladium(II) Complex

et al. 2022

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Phosphinines and donor-substituted phosphinines are of recent interest due to their use in homogeneous catalysis. In this article, a Pd(II) bis(phosphinine) complex was characterised and phosphorus–selenium coupling constants were used to assess the donor properties of the diphenylphosphine substituents of phosphinine ligands to promote their further use in catalysis. The selenation of 2,5-bis(diphenylphosphino)-3,6-dimethylphosphinine (5) and 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (6) gave the corresponding phosphine selenides 8 and 9, respectively, leaving the phosphinine ring intact. Multinuclear NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction confirmed the oxidation of all the diphenylphosphine substituents with 1JP-Se coupling constants determined to be similar to SePPh3, indicating that the phosphinine rings were electronically similar to phenyl substituents. Solutions of 6 were found to react with oxygen slowly to produce the phosphine oxide 10 along with other by-products. The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (4) with [PdCl2(COD)] gave the chelating dichloropalladium(II) complex, as determined by multinuclear NMR spectroscopy, mass spectrometry and an elemental analysis. The molecular structure of the intermediate 2 in the formation of 4,6-di(tert-butyl)-1,3,2-diazaphosphinine (3) was also determined, which confirmed the structure of the diazaphosphacycle P(Cl){N=C(tBu)CH=C(tBu)-N(H)}.

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“…88 The study into the comparative ligating properties of derivative of phosphabenzene, PC 5 H 2 Bu t 3 , and triphosphabenzenes, P 3 C 3 Bu t 3 , has demonstrated that the mono-phosphorus compound is a better s-donor that the tri-phosphorus analogue. 89 An investigation has been reported into a number of known and novel cyclopentadienyl-substituted phosphine ligands. 90 Also reported has been the use of simple cyclodiphosphazanes as probes in reactions such as the Mitsunobu and phosphine-catalysed reaction.…”

Section: Phosphorusmentioning

confidence: 99%