Synthesis, structures and reactivity of bis(iminophosphorano)methanide chelate complexes with transition metal of cobalt, nickel, palladium and iridium

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

doi:10.1016/j.poly.2019.04.060

Cited by 6 publications

(8 citation statements)

References 62 publications

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“…Zhao and co-workers recently reported a study on the reactivity of [C(Ph 2 PNSiMe 3 ) 2 Li 2 ] 2 ( 6a ) with group 9 and 10 transition metal (cobalt, nickel, iridium, and palladium) precursors . The transmetalation reactions of dilithium methandiide complex 6a with 2 equiv of [Co(PPh 3 ) 3 Cl], [Ni(DME)Cl 2 ], and [Ni(DME)Br 2 ] in THF at room temperature resulted in the formation of dimeric bis(phosphinimino)methanide complexes of the compositions [{CH(Ph 2 PNSiMe 3 ) 2 }Co( μ- Cl)] 2 ( 61 ) and [{CH(Ph 2 PNSiMe 3 ) 2 }Ni( μ- Cl)] 2 ( 62 ) and the monomeric complex [{CH(Ph 2 PNSiMe 3 ) 2 }NiBr] ( 63 ) in good yields (Scheme ), respectively.…”

Section: D-block Metal Complexessupporting

confidence: 64%

“…In the complexes 61 – 63 , 65 , and 66 , no carbene–metal bond was formed after the reaction with 3a / 6a in situ , and eventually, singly protonated carbon-coordinated compounds were isolated in the solid state. This study suggested that the carbene linked to these transition metals is not stable enough to impede its protonation tendency …”

Section: D-block Metal Complexesmentioning

confidence: 99%

“…34 Therefore, in this Zhao and co-workers recently reported a study on the reactivity of [C(Ph 2 PNSiMe 3 ) 2 Li 2 ] 2 (6a) with group 9 and 10 transition metal (cobalt, nickel, iridium, and palladium) precursors. 84 The transmetalation reactions of dilithium methandiide complex 6a with 2 equiv of [Co(PPh The reactivity of 6a with the group 9 iridium metallic precursor was different from the observed chemistry for cobalt and nickel metals. An unusual iridium complex [{{(C 6 H 4 )-(Ph)PNSiMe 3 )CHP(Ph) 2 NSiMe 3 }Ir(COD)}Li(THF)] ( 64) was obtained when the precursor [Ir(COD)Cl] 2 (COD = cyclooctadiene) reacted with 6a in a 1:1 molar ratio in THF (Scheme 14).…”

Section: D-block Metal Complexesmentioning

confidence: 99%

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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: D-block Metal Complexessupporting

confidence: 64%

Section: D-block Metal Complexesmentioning

confidence: 99%

Section: D-block Metal Complexesmentioning

confidence: 99%

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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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“…Thus, 2 Ni likely retains a monomeric structure in solution. Dimeric species with Ni 2 I (μ-Cl) 2 cores often exhibit spin-pairing because of antiferromagnetic superexchange through the bridging chloride ligands, or potentially via direct Ni–Ni interactions. − …”

Section: Resultsmentioning

confidence: 99%

Late 3d-Transition Metal Complexes Bearing a Bis-Phosphine Borane Ligand, PhB(CH₂P^tBu₂)₂

2022

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The coordination chemistry of a bidentate ambiphilic ligand, PhB(CH2P t Bu2)2 ([BP2 tBu]), is established for a series of Co, Ni, and Cu compounds. The chloride starting materials [BP2 tBu]MCl2 [M = Co (1 Co ), Ni (1 Ni )] and [BP2 tBu]CuCl (2 Cu ) are readily accessed in high yields by the treatment of the corresponding metal chloride salts with [BP2 tBu] in THF solution. The reduction of 1 Ni to [BP2 tBu]NiCl (2 Ni ) was affected by treatment with KC8. In contrast, the corresponding CoI species was not isolable under similar reaction conditions. However, monovalent mesityl complexes of the form [BP2 tBu]M(Mes) [M = Co (3 Co ), Ni (3 Ni ), Cu (3 Cu )] were prepared by the treatment of 1 Co with one equiv of Mes2Mg(THF)2 or by the reaction of 2 M (M = Ni, Cu) with 0.5 equiv of Mes2Mg(THF)2. Modification of the borane moiety in 2 Ni was explored by the treatment of this complex with 4-dimethylaminopyridine (DMAP) to produce [PhB(DMAP)(CH2P t Bu2)2]NiCl (4), which displays distinct features in its UV–visible spectrum compared to 2 Ni . The solid-state molecular structures of most complexes have been determined by single-crystal X-ray diffraction analysis.

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“…We and others 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 ). Thereafter, our laboratory and other groups applied this dimeric organolithium complex and its precursor {CH 2 (Ph 2 PNSiMe 3 ) 2 }, producing a considerable body of interesting chemistry with main-group, transition, noble, and lanthanide metals. 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.…”

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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Synthesis, structures and reactivity of bis(iminophosphorano)methanide chelate complexes with transition metal of cobalt, nickel, palladium and iridium

Cited by 6 publications

References 62 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

Late 3d-Transition Metal Complexes Bearing a Bis-Phosphine Borane Ligand, PhB(CH₂P^tBu₂)₂

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

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Synthesis, structures and reactivity of bis(iminophosphorano)methanide chelate complexes with transition metal of cobalt, nickel, palladium and iridium

Cited by 6 publications

References 62 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

Late 3d-Transition Metal Complexes Bearing a Bis-Phosphine Borane Ligand, PhB(CH2PtBu2)2

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

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Late 3d-Transition Metal Complexes Bearing a Bis-Phosphine Borane Ligand, PhB(CH₂P^tBu₂)₂