A Scandium Metalloligand‐Based Heterobimetallic Pd−Sc Complex: Electronic Tuning Through a Very Short Pd→Sc Dative Bond

Du, Jun; Huang, Zeming; Zhang, Yanan; Wang, Shaowu; Zhou, Shuangliu; Fang, Hanming; Cui, Peng

doi:10.1002/chem.201901424

Cited by 19 publications

(25 citation statements)

References 71 publications

(43 reference statements)

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“…The recent emergence of coordination compounds containing metal–metal bonds between transition metals (TMs) and rare earth (RE) elements, that is, the group 3 metals and the lanthanides (Ln), has inspired their use in diverse applications. − For example, TM–RE bonded complexes are currently being explored for single-molecule magnetism. , In the realm of catalysis, multimetallic cooperativity between rare earth ions and transition metals can elicit beneficial activity in both heterogeneous , and cluster − systems by affecting the catalyst stability, electronics, and/or substrate binding affinity. Even so, direct TM–RE bonds, especially those involving lanthanides, are rarely seen in homogeneous catalysis.…”

Section: Introductionmentioning

confidence: 99%

Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- and Regioselectivity Impacted by the Lewis Acidity and Size of the Support

Ramirez

2020

J. Am. Chem. Soc.

108

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Bimetallic catalysts of nickel(0) with a trivalent rare-earth ion or Ga(III), NiML3 (where L is [iPr2PCH2NPh]−, and M is Sc, Y, La, Lu, or Ga), were investigated for the selective hydrogenation of diphenylacetylene (DPA) to (E)-stilbene. Each bimetallic complex features a relatively short Ni–M bond length, ranging from 2.3395(8) Å (Ni–Ga) to 2.5732(4) Å (Ni–La). The anodic peak potentials of the NiML3 complexes vary from −0.48 V to −1.23 V, where the potentials are negatively correlated with the Lewis acidity of the M(III) ion. Three catalysts, Ni–Y, Ni–Lu, and Ni–Ga, showed nearly quantitative conversions in the semihydrogenation of DPA, with NiYL3 giving the highest selectivity for (E)-stilbene. Initial rate studies were performed on the two tandem catalytic reactions: DPA hydrogenation and (Z)-stilbene isomerization. The catalytic activity in DPA hydrogenation follows the order Ni–Ga > Ni–La > Ni–Y > Ni–Lu > Ni–Sc. The ranking of catalysts by (Z)-stilbene isomerization initial rates is Ni–Ga ≫ Ni–Sc > Ni–Lu > Ni–Y > Ni–La. In operando 31P and 1H NMR studies revealed that in the presence of DPA, the Ni bimetallic complexes supported by Y, Lu, and La form the Ni(η2-alkyne) intermediate, (η2-PhCCPh)Ni(iPr2PCH2NPh)2M(κ2-iPr2PCH2NPh). In contrast, the Ni–Ga resting state is the Ni(η2-H2) species, and Ni–Sc showed no detectable binding of either substrate. Hence, the mechanism of Ni-catalyzed diphenylacetylene semihydrogenation adheres to two different kinetics: an autotandem pathway (Ni–Ga, Ni–Sc) versus temporally separated tandem reactions (Ni–Y, Ni–Lu, Ni–La). Collectively, the experimental results demonstrate that modulating a base-metal center via a covalently appended Lewis acidic support is viable for promoting selective alkyne semihydrogenation.

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Section: Introductionmentioning

confidence: 99%

Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- and Regioselectivity Impacted by the Lewis Acidity and Size of the Support

Ramirez

2020

J. Am. Chem. Soc.

108

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“…Since the first RE–TM bond in (C 5 H 5 ) 2 Y(THF)Re 2 H 7 (PMe 2 Ph) 4 was structurally characterized by Evans and co-workers in 1990, many chemists have studied this important and fundamental field. Representative examples include complexes with RE–Re (RE = Y, La, Sm, Yb, Lu), − RE–Fe (RE = Nd, Yb, Sc, Y, Lu, La, Dy, Ce), − Sm–Co, RE–Ni (RE = Sc, Y, La, Lu), − RE–Pd (RE = Nd, Sc), − and RE–Pt (RE = Sc, Y, Lu) , bonds. In addition, some examples with metal–metal bonds between RE and main-group metals have also been reported. − However, notwithstanding these important discoveries, bimetallic species with a RE–Rh bond are rare and to the best of our knowledge the heterometallic complexes with multiple RE–Rh bonds are unknown.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

et al. 2021

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Although a series of complexes with rare earth (RE) metal−metal bonds have been reported, complexes which have multiple RE−Rh bonds are unknown. Here we present the identification of the first example of a molecule containing multiple RE−Rh bonds. The complex with multiple Ce−Rh bonds was synthesized by the reduction of a d−f heterometallic molecular cluster Ce{N[(CH 2 CH 2 NP i Pr 2 )RhCl(COD)] 3 } with excess potassium-graphite. The oxidation state of Ce in 3a appears to be a mixture of Ce(III) and Ce(IV), which was confirmed by X-ray photoelectron spectroscopy, magnetism, and theoretical investigations (DFT and CASSCF). For comparison, the analogous species with multiple La(III)−Rh and Nd(III)−Rh bonds were also constructed. This study provides a possible route for the construction of complexes with multiple RE metal−metal bonds and an investigation of their potential properties and applications.

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“…15 Although a few of the heterobimetallic Ln−LM (Ln = rare-earth metals) complexes with an ionic Ln−LM bond or weak LM→Ln interactions were known in past decade, 16,17 it has only recently been reported by Lu that the variation of Ni→Ln (Sc, Y, La, and Lu) dative bond with the Ln 3+ ions played a significant role in the alkene or alkyne hydrogenation reactions. 18 We have reported the first heterobimetallic Pd− Sc complex featuring a Pd→Sc dative bond that tuned the electronic property and the reactivity on Pd(0) center, 19 which was further extended to all group 10 metals with a dative LM→ Sc (LM = Ni, Pd, and Pt) bond and versatile coordination modes on LM(0) centers. 20 Interestingly, modification of the ligands simply from phosphinomethylamido [Ph 2 PCH 2 NAd] − (Ad = admantyl) to the phosphinoamido [Ph 2 PNAd] − led to an unexpected FLP-like reactivity irrelevant with the Pd(0) center.…”

Section: ■ Introductionmentioning

confidence: 99%

P–C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward Isonitrile, Nitrile, and Epoxide

Cui

Huang

et al. 2021

Inorg. Chem.

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Protonolysis of β-diketiminato (nacnac) rare-earth metal bis-alkyl complexes L nacnac LnR 2 (THF) (Ln = Y and Lu) with 2 equiv of Ph 2 PNHPh or Ph 2 PCH 2 NHPh afforded the bis-amido complexes L nacnac Y(Ph 2 PNPh) 2 and L nacnac Ln-(Ph 2 PCH 2 NPh) 2 (Ln = Y and Lu). Metalation of the latter complexes with 1 equiv of Ni(COD) 2 led to the isolation of unusual heterobimetallic Ni(II)−Ln(III) complexes formed via P−C bond cleavage of one [Ph 2 PCH 2 NPh] − ligand. Notably, both the imine PhNCH 2 and phosphide Ph 2 P − fragments from the P−C bond cleavage were trapped in the Ni(II)−Ln(III) core with a relatively weak interaction between the two metal centers. The Ni(II)−Y(III) complex have exhibited versatile reactivity, such as coordination of isonitrile to the Ni(II) center, insertion of nitrile with the coordinated imine, and ring-opening of the epoxide by nucleophilic attack from the phosphide group.

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A Scandium Metalloligand‐Based Heterobimetallic Pd−Sc Complex: Electronic Tuning Through a Very Short Pd→Sc Dative Bond

Cited by 19 publications

References 71 publications

Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- and Regioselectivity Impacted by the Lewis Acidity and Size of the Support

Rare-Earth Supported Nickel Catalysts for Alkyne Semihydrogenation: Chemo- and Regioselectivity Impacted by the Lewis Acidity and Size of the Support

Heterometallic Clusters with Multiple Rare Earth Metal–Transition Metal Bonding

P–C Bond Cleavage Induced Ni(II) Complexes Bearing Rare-Earth-Metal-Based Metalloligand and Reactivities toward Isonitrile, Nitrile, and Epoxide

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