NHC‐Stabilized Bis(trimethylsilyl)phosphido Complexes of Pd<sup>II</sup> and Ni<sup>II</sup>

Madadi, Masoumeh; Najafabadi, Bahareh Khalili; Fard, Mahmood Azizpoor; Corrigan, John F.

doi:10.1002/ejic.201500491

Cited by 8 publications

(1 citation statement)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…34 Other works report TM centers (TM = Pd, Ni, or Ru) directly coordinated to the P in the backbone of the BAP ligand arising from the addition of acid chloride substrates to TM-bound bis(trimethylsilyl)phosphides (Scheme 1). 35,36 We sought to harness the reactivity of BAP ligands towards uranium, as BAP ligands combine the attributes of an Acac ligand with the spectroscopic benefits resulting from the presence of a phosphorus atom. The impetus is to provide stabilization via the electronically and geometrically flexible phosphorus atom, as well as to provide a spectroscopic handle to aid in the synthesis and characterization of molecular uranium complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

Homoleptic Uranium–Bis(acyl)phosphide Complexes

et al. 2022

View full text Add to dashboard Cite

The first uranium bis(acyl)phosphide (BAP) complexes were synthesized from the reaction between sodium bis(mesitoyl)phosphide (Na( mes BAP)) or sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na( tripp BAP)) and UI3(1,4-dioxane)1.5. Thermally stable, homoleptic BAP complexes were characterized by single-crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy, when appropriate, for the elucidation of the electronic structure and bonding of these complexes. EPR spectroscopy revealed that the BAP ligands on the uranium center retain a significant amount of electron density. The EPR spectrum of the trivalent U( tripp BAP) 3 has a rhombic signal near g = 2 (g 1 = 2.03; g 2 = 2.01; and g 3 = 1.98) that is consistent with the EPR-observed unpaired electron being located in a molecular orbital that appears ligand-derived. However, upon warming the complex to room temperature, no resonance was observed, indicating the presence of uranium character.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Homoleptic Uranium–Bis(acyl)phosphide Complexes

et al. 2022

View full text Add to dashboard Cite

show abstract

[Ni(NHC)₂] as a Scaffold for Structurally Characterized trans [H−Ni−PR₂] and trans [R₂P−Ni−PR₂] Complexes

Sabater

Schmidt

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

The addition of PPh 2 H, PPhMeH, PPhH 2 , P(para-Tol)H 2 , PMesH 2 and PH 3 to the two-coordinate Ni 0 Nheterocyclic carbene species [Ni(NHC) 2 ] (NHC = IiPr 2 , IMe 4 , IEt 2 Me 2 ) affords a series of mononuclear, terminal phosphido nickel complexes. Structural characterisation of nine of these compounds shows that they have unusual trans [HÀ NiÀ PR 2 ] or novel trans [R 2 PÀ NiÀ PR 2 ] geometries. The bis-phosphido complexes are more accessible when smaller NHCs (IMe 4 > IEt 2 Me 2 > IiPr 2 ) and phosphines are employed. PÀ P activation of the diphosphines R 2 PÀ PR 2 (R 2 = Ph 2 , PhMe) provides an alternative route to some of the [Ni(NHC) 2 (PR 2 ) 2 ] complexes.DFT calculations capture these trends with PÀ H bond activation proceeding from unconventional phosphine adducts in which the H substituent bridges the NiÀ P bond. PÀ P bond activation from [Ni(NHC) 2 (Ph 2 PÀ PPh 2 )] adducts proceeds with computed barriers below 10 kcal mol À 1 . The ability of the [Ni(NHC) 2 ] moiety to afford isolable terminal phosphido products reflects the stability of the NiÀ NHC bond that prevents ligand dissociation and onward reaction.

show abstract

Introducing the Bis(mesitoyl)phosphide Ligand into Dinuclear Trivalent Rare Earth Metal Coordination Chemistry

Deshapriya,

Delano,

Demir

2024

ChemPlusChem

View full text Add to dashboard Cite

Anionic ancillary ligands play a critical role in the construction of rare earth (RE) metal complexes due to the large influence on the stability of the molecule and engendering emergent electronic properties that are of interest in a plethora of applications. Supporting ligands comprising oxygen donor atoms are highly pursued in RE chemistry owing to the high oxophilicity innate to these ions. The scarcely employed bis(acyl)phosphide (BAP) ligands feature oxygen coordination sites and contain a phosphide backbone rendering it attractive for RE‐coordination chemistry. Here, we integrate bis(mesitoyl)phosphide (mesBAP) as an ancillary ligand into REIII chemistry to generate the first dinuclear trivalent RE complexes containing BAP ligands; [{mesBAP}2RE(THF)(μ‐Cl)]2 (RE = Y, (1), Gd (2), and Dy (3); THF = tetrahydrofuran). Each RE center is ligated to two monoanionic mesBAP ligands, one THF molecule and one chloride ion. All three molecules were characterized through single‐crystal X‐ray diffraction, 31P NMR, IR and UV‐Vis spectroscopy. 31P, 1H and 13C NMR on the diamagnetic yttrium congener 1 confirm asymmetric ligand coordination. DFT calculations conducted on 2 provided insight into the electronic structure. The magnetic properties of 2 and 3 were investigated via SQUID magnetometry. The GdIII ions exhibit weak antiferromagnetic coupling, corroborated by DFT results.

show abstract

NHC‐Stabilized Bis(trimethylsilyl)phosphido Complexes of Pd^II and Ni^II

Cited by 8 publications

References 40 publications

Homoleptic Uranium–Bis(acyl)phosphide Complexes

Homoleptic Uranium–Bis(acyl)phosphide Complexes

[Ni(NHC)₂] as a Scaffold for Structurally Characterized trans [H−Ni−PR₂] and trans [R₂P−Ni−PR₂] Complexes

Introducing the Bis(mesitoyl)phosphide Ligand into Dinuclear Trivalent Rare Earth Metal Coordination Chemistry

Contact Info

Product

Resources

About

NHC‐Stabilized Bis(trimethylsilyl)phosphido Complexes of PdII and NiII

Cited by 8 publications

References 40 publications

Homoleptic Uranium–Bis(acyl)phosphide Complexes

Homoleptic Uranium–Bis(acyl)phosphide Complexes

[Ni(NHC)2] as a Scaffold for Structurally Characterized trans [H−Ni−PR2] and trans [R2P−Ni−PR2] Complexes

Introducing the Bis(mesitoyl)phosphide Ligand into Dinuclear Trivalent Rare Earth Metal Coordination Chemistry

Contact Info

Product

Resources

About

NHC‐Stabilized Bis(trimethylsilyl)phosphido Complexes of Pd^II and Ni^II

[Ni(NHC)₂] as a Scaffold for Structurally Characterized trans [H−Ni−PR₂] and trans [R₂P−Ni−PR₂] Complexes