Organometalloidal derivatives of the transition metals

Pannell, Keith H.; Läppert, Michael F.; Stanley, Keith

doi:10.1016/s0022-328x(00)89364-x

Cited by 30 publications

(5 citation statements)

References 19 publications

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“…2 The potential for stabilizing metal-allyl interactions through the use of trialkyland triaryl-silyl substituents was first identified by Pannell and Lappert in 1976, who reported a series of transition metal s-and p-(silyl-allyl) complexes of general formula [(silyl-allyl)M(CO) x Cp y ] (M = Mn, Fe, Co, Mo, W) or [(silyl-allyl)MCl] 2 (M = Ni, Pd). 40 The bonding modes of the ligands in these heteroleptic silyl-allyl compounds were determined by spectroscopic methods, although no crystallographic studies were carried out. The stabilizing influence of the silyl substituents became strikingly apparent through the synthesis of the homoleptic bis(silyl-allyl)nickel(II) complex [Ni(2-Me 3 SiC 3 H 3 ) 2 ] (36) according to Scheme 12.…”

Section: Scheme 11 5 Transition Metal Silyl-allyl Complexesmentioning

confidence: 99%

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The coordination chemistry of silyl-substituted allyl ligands

Solomon

Layfield

2010

Dalton Trans.

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Metal allyl complexes in which the ligands carry bulky silyl substituents frequently show stability that cannot be achieved with unsubstituted analogues. As a result, it has been possible to characterize a large family of structurally diverse metal silyl-allyls from the s-, p-, d- and f-blocks of the Periodic Table, and to study the coordination chemistry of compounds that often have no counterparts without bulky substituents. The fact that the majority of compounds discussed in this Perspective have been published since 2000 reflects the newness of the area, and the article summarizes the main developments in the structural chemistry of metal silyl-allyls and also selected synthetic and catalytic applications. Although organometallic chemistry is often regarded as transcending traditional boundaries between 'organic' and 'inorganic' chemistry, an understanding persists that those working in the field can be labelled 'inorganic organometallic' chemists or 'organic organometallic' chemists. It is hoped that chemists from a broad range of backgrounds will be able to use this review as an entry point to an exciting new direction in metal allyl chemistry.

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Section: Scheme 11 5 Transition Metal Silyl-allyl Complexesmentioning

confidence: 99%

“…Scheme 12A series of articles by Bochmann 42,43 and by Hanusa 44-47 reported the synthesis and crystallographic characterization of the family of 3d bis(silyl-allyl) complexes [M{C 3 H 3 (SiMe 3 ) 2 } 2 ] with M = Cr(38), Fe(39), Co(40) and Ni(41). Compounds 38-41 were prepared by simple salt metathesis reactions according to Scheme 13.…”

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confidence: 99%

The coordination chemistry of silyl-substituted allyl ligands

Solomon

Layfield

2010

Dalton Trans.

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“…Mono-silylated allyl ligands were first reported by Lappert et al to give access to a variety of transition metal complexes. 10 Fraenkel et al presented the synthesis of the lithium salt of bis-silylated ligand [1,3-(SiMe 3 ) 2 C 3 H 3 ] − . 11 The introduction of [1,3-(SiMe 3 ) 2 C 3 H 3 ] − ligands to alkaline earth metal chemistry by Hanusa et al enabled the isolation of complexes of the general formula [M{1,3-(SiMe 3 ) 2 C 3 H 3 } 2 (L) n ] (M/L/n = Be/ Et 2 O/1; 12 Mg/THF/2; 13 Ca/THF/2; 14 Sr/THF/2 15 ).…”

Section: Introductionmentioning

confidence: 99%

“…13 The isolation of a series of silylated allyl complexes as well as the parent bis(allyl)metal 16,17 complexes allowed exploration of the preferred coordination modes of the allyl ligand. [10][11][12][13][14][15] However, the parent strontium and barium compounds [M(C 3 H 5 ) 2 (L) n ] remained elusive.…”

Section: Introductionmentioning

confidence: 99%

Allyl strontium compounds: synthesis, molecular structure and properties

et al. 2012

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The synthesis and attempted isolation of neutral bis(allyl)strontium [Sr(C(3)H(5))(2)] (1) resulted in the isolation of potassium tris(allyl)strontiate K[Sr(C(3)H(5))(3)] (2). In situ generated 1 shows a pronounced Brønsted basicity, inducing polymerisation of THF. Ate complex 2 crystallises as [K(THF)(2){Sr(C(3)H(5))(3)}(THF)](∞) (2·(THF)(3)). The salt-like solid state structure of 2·(THF)(3) comprises a two-dimensional network of (μ(2)-η(3):η(3)-C(3)H(5))(-) bridged potassium and strontium centres. Synthesis of allyl complexes 1 and 2 utilised SrI(2), [Sr(TMDS)(2)] (3) (TMDS = tetramethyldisilazanide), and [Sr(HMDS)(2)] (HMDS = hexamethyldisilazanide) as strontium precursors. The solid state structure of previously reported [Sr(TMDS)(2)] (3) was established by X-ray single crystal analysis as a dissymmetric dimer of [Sr(2)(TMDS)(4)(THF)(3)] (3·(THF)(3)) with multiple Si-HSr agostic interactions. The presence of ether ligands (THF, 18-crown-6) influenced the Si-HSr resonances in the NMR spectra of the amido complex 3.

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“…[2] In a coordination chemistry setting, despite their widespread use in catalysis, allyl complexes of transition metals are notorious for their thermal instability and air-sensitivity. [3] In contrast, silyl-substituted allyl ligands have allowed access to a broad range of kinetically stabilized, isolable allyl complexes of d-, [4][5][6][7][8][9][10][11][12] f- [13][14][15][16][17][18][19][20] and p-block, [21,22] metals. Whereas structural characterization of metal allyl compounds featuring allyl ligands with low steric demands has been rare, in many cases it has been possible to structurally characterize silylsubstituted metal allyl complexes by X-ray crystallography.…”

Section: Introductionmentioning

confidence: 99%

Alkali Metal Complexes of Silyl‐Substituted ansa‐(Tris)allyl Ligands: Metal‐, Co‐Ligand‐ and Substituent‐Dependent Stereochemistry

et al. 2009

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The structures of alkali metal complexes of silyl-substituted ansa-tris (allyl) [endo,exo] stereochemistries. The trisodium complex [L 2 Na{Na-(tmeda)} 2 ] 2 (6) consists of a hexa(allylsodium) macrocycle that aggregates as a result of cation-π interactions between the phenyl substituents and the sodium cations. An attempt to prepare the tripotassium complex of L 1 resulted in the formation of the bimetallic potassium/lithium complex

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Organometalloidal derivatives of the transition metals

Cited by 30 publications

References 19 publications

The coordination chemistry of silyl-substituted allyl ligands

The coordination chemistry of silyl-substituted allyl ligands

Allyl strontium compounds: synthesis, molecular structure and properties

Alkali Metal Complexes of Silyl‐Substituted ansa‐(Tris)allyl Ligands: Metal‐, Co‐Ligand‐ and Substituent‐Dependent Stereochemistry

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