A novel heterobidentate chiral phosphine and its coordination chemistry in transition metal clusters

Tomashevskaya, M. M.; Tunik, Sergey P.; Podkorytov, Ivan S.; Heaton, Brian T.; Iggo, Jonathan A.; Haukka, Matti; Pakkanen, Tapani A.; Pirilä, Päivi; Pursiainen, Jouni

doi:10.1016/j.jorganchem.2007.03.008

Cited by 10 publications

(1 citation statement)

References 58 publications

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“…However, there is only one example of a symmetrically bridging Nheterocyclic phosphide ligand in the literature, an Os−Rh cluster in which the NHP unit symmetrically bridges two Os centers. 22 There are, on the other hand, several examples of metal complexes containing acyclic μ-P(NR 2 ) 2 − ligands that bridge in an asymmetric, μ-phosphido fashion. 23−28 Since our NHP-containing diphosphine pincer ligand has already proven to asymmetrically bridge Pd and Pt centers in homobimetallic compounds 3 and 4, we now turn our attention to other possible binding modes as a phosphido bridging ligand in both homo-and heterobimetallic as well as trimetallic complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

et al. 2013

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By incorporating an N-heterocyclic phosphenium/phosphide (NHP) ligand into a chelating pincer ligand framework (PPP(+)/PPP(-)), we have elucidated several different and unprecedented binding modes of NHP ligands in homobimetallic, heterobimetallic, and trimetallic metal complexes. One-electron reduction of the previously reported (PPP)(-)/M(II) complexes (PPP)M-Cl (M = Pd (1), Pt (2)) results in clean formation of the symmetric homobimetallic M(I)/M(I) complexes [(μ-PPP)Pd]2 (5) and [(μ-PPP)Pt]2 (6). The tridentate NHP ligand has also been utilized as a bridging linker in the M/Co heterobimetallic compounds (OC)3Co(u-PPP)M(CO) (M = Pd (7), Pt (8)), synthesized via salt elimination from mixtures of 1 and 2 and Na[Co(CO)4]. Furthermore, an NHP-bridged trimetallic complex (PPP)2Pd3Cl2 (9) can be synthesized in a manner similar to precursor 1 (Pd(PPh3)4 + (PPP)Cl) via careful adjustment of reaction stoichiometry. Examination of the interatomic distances and angles in complexes 5-9, in tandem with density functional theory calculations have been used to evaluate and characterize the bonding interactions in these complexes.

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Section: ■ Introductionmentioning

confidence: 99%

Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

et al. 2013

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Selective CH Bond Functionalization of 2‐(2‐Thienyl)pyridine by a Rhodium N‐Heterocyclic Carbene Catalyst

et al. 2014

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[Rh(μ‐Cl)(H)2(IPr)]2 (IPr=1,3‐bis‐(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) catalyzes the selective functionalization of 2‐(2‐thienyl)pyridine efficiently with a range of alkenes and internal alkynes. A catalytic cycle is proposed on the basis of the identification of key reaction intermediates and the study of their reactivity by NMR spectroscopy. Theoretical calculations at the DFT level support that the reaction proceeds by initial κ1N coordination of 2‐(2‐thienyl)pyridine followed by the loss of H2 to afford the active catalyst. Subsequently, cyclometalation of 2‐(2‐thienyl)pyridine, coordination of the unsaturated substrate (alkyne or alkene) at the vacant position trans to the hydride, and reductive elimination of the thiophene moiety occur. Finally, cyclometalation of the thiophene moiety renders the hydride cis to the unsaturated substrate, which leads to migratory insertion into the RhH bond and subsequent reductive elimination of the functionalized product.

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Structure, Stereochemistry and Dynamics of Tetranuclear Polyhydride Clusters Containing Chiral Heterobidentate Phosphanes

Ponomarenko

Krupenya

Grachova

et al. 2009

Zeitschrift anorg allge chemie

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A novel chiral phosphane (S)‐2‐(4‐isopropyl‐2‐oxazoline‐2‐yl)phenyl‐di‐N‐pyrrolylphosphane (S‐PyrPOx) based on asymmetric oxazoline ring has been prepared and characterised. Reaction of this ligand and its phenyl‐substituted analogue (S‐PhPOx) with H4Ru4(CO)12 and H3RhOs3(CO)12 gave substituted derivatives H4Ru4(CO)10(1,1‐PhPOx) (2), H4Ru4(CO)10(1,1‐PyrPOx) (3), and H3RhOs3(CO)10(1,1‐PyrPOx) (4), which were structurally characterised by X‐ray crystallography in solid state and by a variety of multinuclear NMR spectroscopic measurements in solution. In all studied clusters the coordinated ligands form five‐membered chelate rings through phosphorus and nitrogen atoms of oxazoline moiety to afford a novel chiral center associated with the substituted metal atom. The substitution reactions demonstrate extremely high stereoselectivity, which results in formation of only one diastereomer in all three cases to give S,S isomer in 2 and S,R isomer in 3 and 4.

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A novel heterobidentate chiral phosphine and its coordination chemistry in transition metal clusters

Cited by 10 publications

References 58 publications

Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

Selective CH Bond Functionalization of 2‐(2‐Thienyl)pyridine by a Rhodium N‐Heterocyclic Carbene Catalyst

Structure, Stereochemistry and Dynamics of Tetranuclear Polyhydride Clusters Containing Chiral Heterobidentate Phosphanes

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