Structure and bonding patterns in heterometallic organometallics with linear Ln–Pd–Ln motifs

Cemortan, Valeriu; Simler, Thomas; Moutet, Jean‐Claude; Jaoul, Arnaud; Clavaguéra, Carine; Nocton, Grégory

doi:10.1039/d2sc06933d

Cited by 2 publications

(1 citation statement)

References 72 publications

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“…The first example of RE–TM (transition metal) bonding interaction was reported by Beletskaya and co-workers in 1990, which was stabilized by a cyclopentadienyl skeleton . Previously studies have shown that ligands play critical roles in the stabilization of species with M–M bonds. – According to the Hard–Soft Acid–Base theory, nitrogen–phosphorus ligands have been widely used in the construction of species with RE–M bonds, in which the N atom is a hard base which could coordinate with RE centers, while the P atom is a soft base, which could coordinate with TMs …”

Section: Introductionmentioning

confidence: 99%

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Sun,

Shen,

Rajeshkumar

et al. 2023

Inorg. Chem.

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Ligands are known to play a crucial role in the construction of complexes with metal–metal bonds. Compared with metal–metal bonds involving d-block transition metals, knowledge of the metal–metal bonds involving f-block rare-earth metals still lags far behind. Herein, we report a series of complexes with cerium–transition-metal bonds, which are supported by two kinds of nitrogen–phosphorus ligands N[CH2CH2NHPiPr2]3 (VI) and PyNHCH2PPh2 (VII). The reactions of zerovalent group 10 metal precursors, Pd(PPh3)4 and Pt(PPh3)4, with the cerium complex supported by VI generate heterometallic clusters [N{CH2CH2NPiPr2}3Ce(μ-M)]2 (M = Pd, 2 and M = Pt, 3) featuring four Ce–M bonds; meanwhile, the bimetallic species [(PyNCH2PPh2)3Ce-M] (M = Ni, 5; M = Pd, 6; and M = Pt, 7) with a single Ce–M bond were isolated from the reactions of the cerium precursor 4 supported by VII with Ni(COD)2, Pd(PPh3)4, or Pt(PPh3)4, respectively. These complexes represent the first example of species with an RE–M bond between Ce and group 10 metals, and 2 and 3 contain the largest number of RE–M donor/acceptor interactions ever to have been observed in a molecule.

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Section: Introductionmentioning

confidence: 99%

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Sun,

Shen,

Rajeshkumar

et al. 2023

Inorg. Chem.

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Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–Pt^IV-Alkyl Complexes

Tricoire,

Danoun,

Nocton

2024

Inorg. Chem.

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This article focuses on the synthesis of heterobimetallic complexes of lanthanide and platinum. It describes the synthesis of the Cp*Yb(bipym)PtMe2 complex and its characterization, followed by its reactivity with oxidants, giving access to various Pt + IV compounds of trismethyl (PtMe3) and tetramethyl (PtMe4) fragments. Characterization of the electronic properties of the complexes by magnetic measurements demonstrated that the tetramethyl complex possesses a singlet ground state. The trismethyl fragments, on the other hand, have a ground state that evolves as a function of the ligand saturating the coordination sphere: a singlet for triflate and pyridine and a triplet for iodine, demonstrating the capacity for simple tuning of the electronic structure of these complexes. While the addition of B(C6F5)3 to the platinum + II bis methyl complex leads to FLP-like reactivity triggering THF opening, reactivity with [Ph3C]+[BPh4]− leads to oxidation of the bipym ligand. Furthermore, the light reactivity of the tetramethyl complex indicated the possible transfer of a methyl group, leading to functionalization of the bridging bipym ligand.

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Structure and bonding patterns in heterometallic organometallics with linear Ln–Pd–Ln motifs

Abstract: Complexes with short intermetallic distances between transition metal fragments and lanthanide (Ln) fragments are fascinating objects of study, owing to the ambiguity of the nature of the interaction. The addition...

Cited by 2 publications

References 72 publications

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–Pt^IV-Alkyl Complexes

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Structure and bonding patterns in heterometallic organometallics with linear Ln–Pd–Ln motifs

Abstract: Complexes with short intermetallic distances between transition metal fragments and lanthanide (Ln) fragments are fascinating objects of study, owing to the ambiguity of the nature of the interaction. The addition...

Cited by 2 publications

References 72 publications

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Heterometallic Clusters with Cerium–Transition-Metal Bonding Supported by Nitrogen–Phosphorus Ligands

Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–PtIV-Alkyl Complexes

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Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–Pt^IV-Alkyl Complexes