Double .beta.-addition of electrophiles to acetylide ligands

Mayr, Andreas; Schaefer, K.; Huang, Esther Y.

doi:10.1021/ja00317a074

Cited by 51 publications

(11 citation statements)

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“…As expected for these octahedral complexes, the IR spectra show three bands for the carbonyl groups which are considerably shifted to lower wavenumbers with respect to those for corresponding vinylidene complexes. [7] The results of the X-ray structure analysis of 1 b (Figure 1) show that the molecule adopts C 1 symmetry in the crystal. [8] The W(CO) 5 moiety exhibits C-W-C angles of about 908 and very similar WÀC and CÀO distances, and thus displays approximately C 4v symmetry.…”

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confidence: 99%

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Synthesis and Structure of the First Terminal Borylene Complexes

Braunschweig¹,

Kollann²,

Englert³

1998

Angewandte Chemie International Edition

198

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A nearly linear arrangement is observed for the three atoms in the central W-B-N unit of the tungsten complex [(CO) WBN(SiMe ) ] (1) in the crystal (W-B-N 177.9°; see picture). This compound along with its Cr analogue represent the first examples of terminal borylene complexes with a two-coordinate metal-bound boron atom. The geometries of the axial and equatorial CO groups in 1 are similar, and thus indicate that there is no trans effect of the borylene ligand.

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confidence: 99%

“…Structure of 1 b in the crystal (ellipsoids at the 30 % probability level; the hydrogen atoms are shown with arbitrary radii) [17]. Selected bond lengths [] and angles[8]: WÀB 2.151(7), BÀN 1.338(8); W-B-N 177.9(5).…”

mentioning

confidence: 99%

Synthesis and Structure of the First Terminal Borylene Complexes

Braunschweig¹,

Kollann²,

Englert³

1998

Angewandte Chemie International Edition

198

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“…[411 The final absorbance apparently corresponds to that of the product, [MoH,Cl,(dppe),] (see later discussion), but the initial absorbance is slightly lower than that expected for trans-[MoH(q3-C,H,)(dppe),l. The difference between the expected and the observed initial absorbance is independent of the concentration of acid. The reaction exhibits a first-order dependence on the concentration of complex and a dependence on the concentration of HC1 as described by Equation (22). These simple kinetics are to be contrasted with the hydrocarbon product distribution shown in Figure 7, which changes quite dramatically in the acid concentration range over which the kinetics are defined.…”

Section: Formation Of Propene and Propynementioning

confidence: 96%

Protonation of Unsaturated Hydrocarbon Ligands: Regioselectivity, Stereoselectivity, and Product Specificity

Henderson

1996

Angew. Chem. Int. Ed. Engl.

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Understanding the mechanisms of protonation of hydrocarbon ligands is fundamental t o a wide range of chemistry including organic synthesis, organometallic chemistry, and even bioinorganic chemistry. Protonation at carbon or metal sites is often slow. with the result that in species containing both types of sites, initial protonation can be at either the metal or the carbon. This has fundamental consequences on the reactivity of hydrocarbon ligands, which are highlighted in this article. In particular, many reactions are apparently the result of a regioselective protonation on the basis of structural analysis of the isolated products. In fact, these products are often formed by an indirect route involving kinetically controlled protonation at the "wrong" site followed by rearrangement to form the thermodynamically controlled, apparently regioselective. product. Other aspects of the protonation mechanisms of complexes containing hydrocarbon ligands are discussed. with an emphasis on the manner in which competitive protonation at metal or ligand can be exploited to select which hydrocarbon is produced and to control the stereochemistry of the hydrocarbon.

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“…380 The dialkyl derivatives [W(CO) 5 (=C=CBu l R)] (R = Me or Et) are also known and are formed by P-additions to alkynide ligands. 324 Vinylidene complexes react with electron-rich alkynes to form cyclobutenylidene derivatives (Equation (36)). Oxidative cleavage o f the cyclobutenylidene gives the corresponding cyclobutenones.…”

Section: Vinylidenes and Related Speciesmentioning

confidence: 99%

Hexacarbonyls and Carbonyl Complexes of Carbon σ-Bonded Ligands of Chromium, Molybdenum and Tungsten

Winter

1995

Comprehensive Organometallic Chemistry II

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Double .beta.-addition of electrophiles to acetylide ligands

Cited by 51 publications

References 1 publication

Synthesis and Structure of the First Terminal Borylene Complexes

Synthesis and Structure of the First Terminal Borylene Complexes

Protonation of Unsaturated Hydrocarbon Ligands: Regioselectivity, Stereoselectivity, and Product Specificity

Hexacarbonyls and Carbonyl Complexes of Carbon σ-Bonded Ligands of Chromium, Molybdenum and Tungsten

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