Synthesis and structures of (dialkylsilylene)bis(phosphine)-nickel, palladium, and platinum complexes and (η6-arene)(dialkylsilylene)nickel complexes

Watanabe, Chieko; Inagawa, Yuichiro; Iwamoto, Takeaki; Kira, Mitsuo

doi:10.1039/c0dt00415d

Cited by 59 publications

(36 citation statements)

References 48 publications

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“…The Ni–Sn bond length changes in these examples from donor to acceptor stannylene from 2.398(1) to 2.674(1) Å . Literature examples for typical stannylene–nickel coordination exhibit Ni–Sn bond lengths that are comparable to the donor–stannylene interaction. ,, The coordination of the nickel atom at the aromatic ring of the terphenyl moiety is comparable with the xanthene literature example and other benzene Ni(0) complexes. ,− …”

Section: Resultsmentioning

confidence: 85%

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

et al. 2018

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1,1'-Dilithioferrocene was reacted with 2 equiv of isopropyl (Ar*) or methyl (Ar') substituted terphenyl tin(II) chloride. Reaction product 1, carrying the bulkier terphenyl substituent Ar*, displays a bis(stannylene) structure in the solid state without formation of a tin-tin bond. Temperature-dependent solution Sn NMR spectroscopy, however, revealed a dynamic interplay between bis(stannylene) (100 °C) and cyclic distannene (-80 °C). In contrast to 1, the less bulky Ar' substituent results in a cyclic distannene 2. On the basis of temperature-dependentSn NMR spectroscopy the Sn-Sn bond of compound 2 was preserved up to 100 °C. Both compounds were further characterized by solid-state Sn NMR spectroscopy as well asSn and Fe Mössbauer spectroscopy. 1 reacted as a chelating ligand with nickel and palladium complexes [Ni(cod)] and [Pd(nbe)] (nbe = norbornene). In the resulting coordination compounds the nonstabilized stannylene acts as a donor as well as an acceptor ligand and shows a dynamic switch from donor to acceptor behavior in the monopalladium complex.

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Section: Resultsmentioning

confidence: 85%

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

et al. 2018

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“…The authors conclude that the silylene donor (in 2-7 ) is a strong σ-donor and a weak π-acceptor 12 Additional example reported with coordinated benzene ( 29 Si = 357.2 (Si), −3.4 (SiMe)) 13 Complexes 2-10 and 2-11 exihibit significant back-donation from the metal to the silylene ligand …”

Section: Background and Alternate Synthetic Methods For Si–tm Bond Fo...mentioning

confidence: 99%

“… 12 Additional example reported with coordinated benzene ( 29 Si = 357.2 (Si), −3.4 (SiMe)) 13 Complexes 2-10 and 2-11 exihibit significant back-donation from the metal to the silylene ligand 14 DFT calculations for the model complex Me 2 SiPdSiMe 2 indicate a significantly bent Si–Pd–Si in the optimized geometry, due to π-back-donation.…”

Section: Background and Alternate Synthetic Methods For Si–tm Bond Fo...mentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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“…Kira and his group also more recently revealed the potential of 70 to coordinate with nickel and platinum (and other palladium) complexes, affording a further array of group 10 complexes bearing electron-rich phosphane ligands or arenes as supporting ligands [79]. Silylenes belonging to this class are the rarest silicon(II) compounds.…”

Section: Shmentioning

confidence: 97%

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

Blom

Drieß

2013

Structure and Bonding

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*2 Si: (Cp* ¼ η 5 -C 5 Me 5 ), the first isolable Si(II) compound, and later in 1994 with the discovery of the first N-heterocyclic silylene by West and Denk, heralding the beginning of a bourgeoning era in low-valent silicon chemistry. Since these and other key discoveries, massive advances have been made in understanding and elucidating the nature of these reactive compounds, and their ability, for example, to activate small molecules, or behave as ligands in transition metal complexes which can perform a variety of catalytic or stoichiometric transformations. In this chapter, recent advances in silylene chemistry will be presented, with a particular focus on developments in the last 10 years approximately. A key emphasis will rest on the reactivity of isolable silylenes, including their coordination towards metals, with respect to small molecule bond activation, and potential catalytic transformations. Although metalcoordinated silylene complexes have been shown to be catalytically useful in a variety of transformations, metal-free catalysis with silylenes is still a target.

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Synthesis and structures of (dialkylsilylene)bis(phosphine)-nickel, palladium, and platinum complexes and (η6-arene)(dialkylsilylene)nickel complexes

Cited by 59 publications

References 48 publications

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

Cyclic Distannene or Bis(stannylene) with a Ferrocenyl Backbone: Synthesis, Structure, and Coordination Chemistry

Reactions of Hydrosilanes with Transition Metal Complexes

Recent Advances in Silylene Chemistry: Small Molecule Activation En-Route Towards Metal-Free Catalysis

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