Metal-Only Lewis Pairs with Transition Metal Lewis Bases

Bauer, Jürgen; Braunschweig, Holger; Dewhurst, Rian D.

doi:10.1021/cr3000048

Cited by 248 publications

(252 citation statements)

References 144 publications

(183 reference statements)

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“…However, the M-Pb bonding in these complexes was reported to consist almost exclusively of M(d)-Pb(p) dative bonding, making them instead clear-cut cases of unsupported metal-only Lewis pairs (MOLPs). 3 This is in accordance with Marder's earlier report of the dinuclear MOLP complexes [{(Me 3 P) 3 ClM}(m-SnCl 2 )] (M = Rh, Ir). 4 In contrast, the reported Group 4 plumbylene complexes 1b possess planar Pb atoms and classical s donation/p backdonation akin to that found in Fischer carbenes (Scheme 1).…”

supporting

confidence: 92%

σ-Donor–σ-acceptor plumbylene ligands: synergic σ-donation between ambiphilic Pt0 and Pbii fragments

Braunschweig

Damme²,

Dewhurst

et al. 2012

Chem. Commun.

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supporting

confidence: 92%

σ-Donor–σ-acceptor plumbylene ligands: synergic σ-donation between ambiphilic Pt0 and Pbii fragments

Braunschweig

Damme²,

Dewhurst

et al. 2012

Chem. Commun.

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“…60, center bottom), and ZrCl 4 [333]. The richness and the vibrancy of the field are eloquently illustrated in numerous recent reviews which focus not only on the structures of these unusual complexes but also on their intriguing reactivities [151,[334][335][336][337][338].…”

Section: C-3 Direct Quantum-chemical Calculation Of Osmentioning

confidence: 99%

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Karen

McArdle

Takats

2014

Pure and Applied Chemistry

111

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A generic definition of oxidation state (OS) is formulated: "The OS of a bonded atom equals its charge after ionic approximation". In the ionic approximation, the atom that contributes more to the bonding molecular orbital (MO) becomes negative. This sign can also be estimated by comparing Allen electronegativities of the two bonded atoms, but this simplification carries an exception when the more electronegative atom is bonded as a Lewis acid. Two principal algorithms are outlined for OS determination of an atom in a compound; one based on composition, the other on topology. Both provide the same generic OS because both the ionic approximation and structural formula obey rules of stable electron configurations. A sufficiently simple empirical formula yields OS via the algorithm of direct ionic approximation (DIA) by these rules. The topological algorithm works on a Lewis formula (for a molecule) or a bond graph (for an extended solid) and has two variants. One assigns bonding electrons to more electronegative bond partners, the other sums an atom's formal charge with bond orders (or bond valences) of sign defined by the ionic approximation of each particular bond at the atom. A glossary of terms and auxiliary rules needed for determination of OS are provided, illustrated with examples, and the origins of ambiguous OS values are pointed out. An electrochemical OS is suggested with a nominal value equal to the average OS for atoms of the same element in a moiety that is charged or otherwise electrochemically relevant.

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“…Our hypothesis is that when the electron rich iron center of ferrocene and the electropositive metal ion are brought into close proximity, a donor-acceptor interaction takes place between iron and the metal (Bauer et al, 2012). This type of Lewis acid-Lewis base interaction was observed previously with both electrophilic early and late transition metals (Chart 19): Seyferth suggested a weak, dative Fe-to-Pd bond in [Fe( 5 -C5H4S)2]Pd(PPh3) (Seyferth et al, 1983); Akabori later provided a comprehensive study based on [M( 5 -C5H4O)2]M′(PPh3) (M = Fe or Ru, M′ = Pd or Ni) that supported a dative M-M′ interaction (Akabori et al, 1987); Nataro recently reported on the electronic structure of palladium(II) and platinum(II) compounds of 1,1ʹ-bis(phosphino)metallocenes (Gramigna et al, 2013).…”

mentioning

confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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Metal-Only Lewis Pairs with Transition Metal Lewis Bases

Cited by 248 publications

References 144 publications

σ-Donor–σ-acceptor plumbylene ligands: synergic σ-donation between ambiphilic Pt0 and Pbii fragments

σ-Donor–σ-acceptor plumbylene ligands: synergic σ-donation between ambiphilic Pt0 and Pbii fragments

Toward a comprehensive definition of oxidation state (IUPAC Technical Report)

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

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