Reactivity of [{(N3N)W P] towards Gold(I) salts – Synthesis of [{(N3N)W P AuCl] and [{(N3N)W P}2Au][pftb] (pftb = Al(OC(CF3)3)4)

Baláȥs, Gábor; Hautmann, Matthias G.; Seidl, Michael; Scheer, Manfred

doi:10.1016/j.ica.2017.10.010

Cited by 4 publications

(2 citation statements)

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“…We surveyed the literature and selected a range of representative compounds that were structurally characterized, have clear 31 P NMR data, and cover the range of dative single bond phosphines, covalent single bond phosphanides, covalent double bond phosphinidenes, and covalent triple bond phosphidos. In addition to 1 – 4 , this adds an additional 57 complexes to the analysis, spanning Th, Sc, Ti, Zr, Nb, Mo, W, Re, Ru, Os, Co, Rh, Ir, and Ni metals, all computed at the same B3LYP level as 1 – 4 , Table S6. − ,,,,,,,,,− We thus plotted δ iso values vs computed MBOs for a wide range of Th and groups 3–10 of the transition metals, Figure .…”

Section: Resultsmentioning

confidence: 99%

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

Du,

Hurd,

Seed

et al. 2023

J. Am. Chem. Soc.

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We report the use of solution and solid-state 31 P Nuclear Magnetic Resonance (NMR) spectroscopy combined with Density Functional Theory calculations to benchmark the covalency of actinide-phosphorus bonds, thus introducing 31 P NMR spectroscopy to the investigation of molecular f-element chemical bond covalency. The 31 P NMR data for [Th(PH 2 )-and for 4 the largest CSA for any bridging phosphido unit. The B3LYP functional with 50% Hartree−Fock mixing produced spin−orbit δ iso values that closely match the experimental data, providing experimentally benchmarked quantification of the nature and extent of covalency in the Th−P linkages in 1−4 via Natural Bond Orbital and Natural Localized Molecular Orbital analyses. Shielding analysis revealed that the 31 P δ iso values are essentially only due to the nature of the Th−P bonds in 1−4, with largely invariant diamagnetic but variable paramagnetic and spin−orbit shieldings that reflect the Th−P bond multiplicities and s-orbital mediated transmission of spin−orbit effects from Th to P. This study has permitted correlation of Th−P δ iso values to Mayer bond orders, revealing qualitative correlations generally, but which should be examined with respect to specific ancillary ligand families rather than generally to be quantitative, reflecting that 31 P δ iso values are a very sensitive reporter due to phosphorus being a soft donor that responds to the rest of the ligand field much more than stronger, harder donors like nitrogen.

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Section: Resultsmentioning

confidence: 99%

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

Du,

Hurd,

Seed

et al. 2023

J. Am. Chem. Soc.

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“…Yet, crystallization affords the homoleptic carbide-bridged complex, [{(Cy 3 P) 2 Cl 2 RuC} 2 Au]OTf; a practical, alternative, route to the homoleptic complex employs a putative [Au(tht) 2 ] + ion (generated from [AuCl(tht)] and [Ag(tht) 2 OTf]). Interestingly, Scheer reported that phosphide analogues of the carbide-gold complexes, namely [LWP–AuCl] and [{LWP} 2 Au][Al{OC(CF 3 ) 3 } 4 ] (H 3 L = N{CH 2 CH 2 NH(SiMe 3 )} 3 ), form upon metalation of neutral [LWP] …”

Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating L n M−CE x fragments, followed by cleavage of the C−E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide−carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C 1 reagents, engage in cross-coupling reactions, and enact Fischer−Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.

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P atom as ligand in transition metal chemistry: Structural aspects

Conejo

Pastor

Montilla

et al. 2021

Coordination Chemistry Reviews

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Reactivity of [{(N3N)W P] towards Gold(I) salts – Synthesis of [{(N3N)W P AuCl] and [{(N3N)W P}2Au][pftb] (pftb = Al(OC(CF3)3)4)

Cited by 4 publications

References 37 publications

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

Transition Metal Carbide Complexes

P atom as ligand in transition metal chemistry: Structural aspects

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Reactivity of [{(N3N)W P] towards Gold(I) salts – Synthesis of [{(N3N)W P AuCl] and [{(N3N)W P}2Au][pftb] (pftb = Al(OC(CF3)3)4)

Cited by 4 publications

References 37 publications

31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

31P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

Transition Metal Carbide Complexes

P atom as ligand in transition metal chemistry: Structural aspects

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Product

Resources

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Reactivity of [{(N3N)W P] towards Gold(I) salts – Synthesis of [{(N3N)W P AuCl] and [{(N3N)W P}2Au][pftb] (pftb = Al(OC(CF3)3)4)

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order

³¹P Nuclear Magnetic Resonance Spectroscopy as a Probe of Thorium–Phosphorus Bond Covalency: Correlating Phosphorus Chemical Shift to Metal–Phosphorus Bond Order