Mono and bis carbene neodymium(III) spirocyclic complexes with a cumulene carbon metal structure

Li, Jingwei; Zhao, Jianguo; Ma, Guibin; McDonald, Robert; Cavell, Ronald G.

doi:10.1016/j.jorganchem.2019.05.018

Cited by 10 publications

(8 citation statements)

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“…Recently, Ma et al introduced a rare example of a biscarbene neodymium(III) spirocyclic complex with a cumulene carbon metal structure . The biscarbene neodymium organometallic compound [{C(Ph 2 PNSiMe 3 ) 2 } 2 Nd][Li(THF) n ] ( 166 ) was prepared in a one-pot, two-step reaction by the treatment of [{C(Ph 2 PNSiMe 3 ) 2 }Li 2 ] ( 6a ) with NdCl 3 in THF under inert conditions (Scheme ).…”

Section: F-block Metal Complexesmentioning

confidence: 99%

“…In complex 166 , the neodymium metal center is linearly flanked by the two tridentate-chelated PCP carbene ligands (178.21(10)°) with the same bond distances (Nd–C(1) = 2.585(3) and Nd–C(2) = 2.583(3) Å, respectively) and adopts a six-coordinate geometry. The neodymium metal center in complex 167 is coordinated to one spirocyclic tridentate PCP ligand (average Nd–N bond distance of 2.576(2) Å and Nd–C bond distance of 2.7401(17) Å) and two five-membered Cp rings (average Nd–C bond distances of 2.771(2) and 2.786(2) Å) above and below the plane that consists of P1, P2, and Nd atoms with a dihedral angle of 59.08(9)° (Figure a) …”

Section: F-block Metal Complexesmentioning

confidence: 99%

See 1 more Smart Citation

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

Jain,

Karmakar,

Roesky

et al. 2023

Chem. Rev.

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Section: F-block Metal Complexesmentioning

confidence: 99%

Section: F-block Metal Complexesmentioning

confidence: 99%

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

Jain,

Karmakar,

Roesky

et al. 2023

Chem. Rev.

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“…The reactiono f4a with DIC clearly demonstrates its Schrock-carbene-like nucleophiliccharacter. 3; 7:C 1 ÀC2 1.457(2), C2ÀC3 1.441(2),C 3 ÀC4 1.410(3), C4ÀC5 1.445(2), C1ÀO1 1.287 2; 8:C 1 ÀC2 1.469(2), C2ÀC3 1.421(2),C 3 ÀC4 1.468(2),C 1 ÀC4 1.507(2), C13ÀC14 1.405(5), C14ÀC15 1.406 (5),C 15ÀC16 1.407(5), C16ÀC171 .401(6), C17ÀC181.404(6), C18ÀC19 1.401(6), C19ÀC20 1.409 5 When CO was added into the THF solution of 4a at room temperature for 1h,aunique oxycyclopentadienyl (OCp) [23] titanium complex 7 was formed in 79 %i solated yield and structurally characterizedb ys ingle-crystal X-ray structurala nalysis (Scheme3ba nd Figure4b). The new cyclopentadienyl anion moiety in 7 is coordinated to the titaniuma tom in h 5 fashion.…”

Section: Reactivitymentioning

confidence: 99%

“…Examples of Schrock-carbene-like alkylidenes are mainly formed from group 3a nd 4m etals. [4][5][6][7] They are usually unstable and very difficult to access owing to the high negative charges on the carbene carbon atom, and the lack of de lectrons and high de nergy level of the metal center.T hese alkylidene carbonsa re generally stabilized by supporting ligands with strongly stabilizingm oieties, such as P V or S VI substituents at two a-positions of the carbon atoms, which delocalize the charge on the alkylidene carbon. Onlyt wo examples of Schrock-carbene-likeb is-alkylidenes sharing ag roup 4m etal center (Scheme 1b)w ere reported using as imilars tabilizing strategy, in which the stabilizing ligands of two alkylidene carbon atoms adopt the almost perpendicular configuration.…”

Section: Introductionmentioning

confidence: 99%

Cyclic Bis‐alkylidene Complexes of Titanium and Zirconium: Synthesis, Characterization, and Reaction

Zhang

Zhong

et al. 2020

Chemistry A European J

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“…Recently, several lanthanides and uranium nucleophilic carbene complexes containing the NPCPN methanediide pincer carbon and the related SCS (SCS = (Ph 2 PS) 2 C 2– ) ligand were obtained and structurally characterized. In these structures, M–C(carbene) multiple bonds or cumulene-carbon–metal bonds involving 4f and 5f orbitals were determined …”

Section: Introductionmentioning

confidence: 99%

Rare Carbon-Bridged Bimetallic Lanthanide (Nd or Sm) and Tl(I) Geminal Carbon Derivatives of a Bis(iminophosphorano)methanediide

Zhao

Ferguson

et al. 2020

Organometallics

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i d g e d b i s -(iminophosphorano)methanediide complexes [CpNd(Tl){C-(Ph 2 PNSiMe 3 ) 2 }Cl 2 Li(THF) 2 ]•Et 2 O ( 2) and [SmCl 3 Tl{C-(Ph 2 PNSiMe 3 ) 2 }Li(THF) 2 ] 2 (3) were prepared from reactions of the dilithiated bis(iminophosphorano)methanediide [Li 2 L] (1; L = C 2− (Ph 2 PNSiMe 3 ) 2 ) with Nd and Sm chlorides and with CpTl and TlCl, respectively, in THF. Both final products contain coordinated Li linked with Cl bridges. The complexes have been structurally characterized and show that the bridging methanediide backbone carbon of the ligand is substituted with one Tl(I) and one rare-earth atom and has a tetrahedral geometry. The 31 P{ 1 H} NMR spectrum (THF-d 8 ) of 2 shows a broad signal at 13.75 ppm with a two-bond spin−spin coupling ( 2 J Tl−P = 410 Hz), indicating that the C−Tl bond is maintained in solution. The 31 P{ 1 H} NMR spectrum of 3 was less informative because the complex is more paramagnetic, and thus only a very broad single peak was observed. DFT calculations on the model compounds [CpNd(Tl){C(PhMePNSiH 3 ) 2 }Cl 2 Li(THF) 2 ] (2a) and [SmTl{C(PhMePNSiH 3 ) 2 Cl 2 ] 2 (3a), whose crystal structures are based on those for 2 and 3, were performed; the results clearly demonstrate the bonding characteristics among the metal centers (Nd(III), Sm(III), Tl(I)) and bridged carbon. In contrast to most Tl(I) compounds, 2 and 3 are reasonably stable in air; this is attributed to protection of the Tl(I) by some of the phenyl substituents on the phosphorus through π-bonding interactions. X-ray and DFT data indicate that, for 2, Tl(I) is a five-coordinate center through one strong carbene carbon bond and four weak phenyl carbon bonds, while for 3, Tl(I) is six-coordinate through strong carbene carbon and chloride bonds and four weak phenyl carbon bonds. These complexes are the first examples of a single carbon or carbene forming a bridge between the main-group heavy metal Tl(I) and another rare-earth metal.

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Mono and bis carbene neodymium(III) spirocyclic complexes with a cumulene carbon metal structure

Cited by 10 publications

References 51 publications

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

Cyclic Bis‐alkylidene Complexes of Titanium and Zirconium: Synthesis, Characterization, and Reaction

Rare Carbon-Bridged Bimetallic Lanthanide (Nd or Sm) and Tl(I) Geminal Carbon Derivatives of a Bis(iminophosphorano)methanediide

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