A geminal dithallated bis(iminodiphenylphosphorano)methine carbon bridged dimer bound by Tl–Tl interactions

Ma, Guibin; Ferguson, Michael J.; Cavell, Ronald G.

doi:10.1039/c0cc01088j

Cited by 17 publications

(4 citation statements)

References 26 publications

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“…For example, Uhl et al described the synthesis of clusters of Tl[C(SiMe 3 ) 3 ], 17 and Power et al reported monomeric TlAr*, 18 dimeric Ar*Tl−TlAr* , 19 and trimeric (TlAr*) 3 19 as well as the chair-shaped dimeric C 2 Tl 4 methanediide complex. 20 These are all supported by the sterically congested ligand Ar* (=C 6 H 3 -2,6(C 6 H 2 -2,4,6-Pr i 2 ) 2 ). We 21 and others 22 have reported the synthesis, by double deprotonation of the methylene C atoms of the parent ligand, and characterization of the structurally unusual dimeric organolithium complex of dilithiated bis(iminophosphorano)methanediide [Li 2 L] 2 (1; L = C 2− (Ph 2 PNSiMe 3 ) 2 ).…”

Section: Introductionmentioning

confidence: 87%

“…We have previously reported on a series of bimetallic (Cu, Rh, Pd, and Tl) geminally carbon-bridged complexes., ,− However, in comparison to Cu, Rh, and Pd, we realized that the Tl(I) dimeric methanediide complex is very unstable in air and even decomposes under an inert atmosphere. In our previous examples of complexes of Sm and Nd, the reaction of {CH 2 (Ph 2 PNSiMe 3 ) 2 } with [Sm(NCy 2 ) 3 (THF)] formed a Sm complex with a carbene/CSm(III) double bond and the reaction of NdCl 3 with {CLi 2 (Ph 2 PNSiMe 3 ) 2 } formed a cumulene (CNdC) carbene carbon metal structure; these two complexes are reasonably stable in air and stable for a long time without decomposition in an inert atmosphere.…”

Section: Introductionmentioning

confidence: 90%

“…For a long time structurally characterized carbon-bound Tl(I) organometallics were limited to systems containing the cyclopentadienyl ligand, − but recent work has identified σ-bound carbon derivatives of Tl(I). For example, Uhl et al described the synthesis of clusters of Tl[C(SiMe 3 ) 3 ], and Power et al reported monomeric TlAr*, dimeric Ar*Tl–TlAr* , and trimeric (TlAr*) 3 as well as the chair-shaped dimeric C 2 Tl 4 methanediide complex . These are all supported by the sterically congested ligand Ar* (=C 6 H 3 -2,6(C 6 H 2 -2,4,6-Pr i 2 ) 2 ).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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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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“…In addition, there are weak Tl–phenyl contact interactions (average Tl···C = 3.378 Å). These interactions are responsible for stabilizing the dimer …”

Section: P-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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Bi‐ and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand

Burgert,

Sun,

Hauser

et al. 2024

Chemistry An Asian Journal

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Herein, we report the synthesis of a novel ferrocenyl functionalized bis(phosphinimino)methane ligand (CH2(PPh2NFc)2). Deprotonation of CH2(PPh2NFc)2 with KN(SiMe3)2 gave the dimeric species [K{CH(PPh2NFc)2}]2, which was further reacted with ECl2 (E = Ge, Sn) to yield the tetrylene compounds [{CH(PPh2NFc)2}ECl]. The ligand and the resulting tetrylenes were examined for their redox chemical properties by cyclovoltammetric measurements. Furthermore, the reaction of the tetrylenes [{CH(PPh2NFc)2}ECl] with [AuC6F5(tht)] resulted in the bimetallic complexes [{(AuC6F5)CH(PPh2NFc)2}ECl] with an unusual Au coordination on the ligand backbone.

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A geminal dithallated bis(iminodiphenylphosphorano)methine carbon bridged dimer bound by Tl–Tl interactions

Cited by 17 publications

References 26 publications

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

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

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

Bi‐ and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand

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