Indenyl carbametallaboranes

Lewis, Z. G.; Welch, Alan J.

doi:10.1016/0022-328x(92)83419-i

Cited by 24 publications

(3 citation statements)

References 12 publications

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“…The isoelectronic series 1 − 3 is well characterized, in terms of both 11 B NMR spectra and X-ray crystallography of suitable crystals . From the 4d congeners 4 − 6 , to our knowledge, only the Pd derivative 16 has been reported . For each compound, we have located all stationary points for rotation about the axis passing through B10 and B10‘, using the dihedral angle B8‘−M−B10−B8 ( θ ) as a measure for this rotation (see Scheme for numbering).…”

Section: Resultsmentioning

confidence: 99%

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

et al. 2006

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A density functional study at the BP86 level is presented for metal bis(dicarbollides), [3-M-(1,2-C 2 B 9 H 11 ) 2 ] n (M/n ) Fe,Ru/2-, Co,Rh/1-, Ni,Pd/0), as well as selected mixed-and half-sandwich complexesAvailable experimental 11 B NMR chemical shifts of these complexes with closo structure of the metallacarborane moiety are reproduced reasonably well at the GIAO-B3LYP/II′ level, with mean absolute deviations of ca. 3 ppm (over a chemical-shift range of ca. 50 ppm). The potential usefulness of this computational protocol for assignments and structural refinements of transition-metal-containing heteroboranes is illustrated in an application to 14-vertex closo clusters [1,14-{(arene)Ru} 2 (x,y-C 2 B 10 H 12 ), where the C-substitution pattern in the carborane moiety is identified.

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Section: Resultsmentioning

confidence: 99%

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

et al. 2006

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“…18 We therefore sought to complex rac-3 under conditions where the sulfur was likely to coordinate to the metal prior to π-complexation, ensuring this complexation takes place syn to the sulfur. Lewis and Welch 19 have reported the formation of the complex [(C 9 H 7 )RhCl 2 ] x on heating a solution of indene and rhodium trichloride trihydrate in methanol under reflux, and these conditions were thought likely to be conducive to our aims. On heating a mixture of the ligand rac-3 and rhodium trichloride trihydrate (1 equiv) in methanol under reflux, a yellow-orange precipitate initially formed (presumably sulfur-coordinated rhodium species; the 1 H NMR spectrum of the isolated solid was very broad and complex, and the material not studied further), which on continued heating gradually dissolved to afford a dark red-brown solution.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

et al. 2012

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Axially chiral rac-1-(2-methyl-1H-inden-3-yl)-2-(methylsulfanyl)naphthalene (rac-3) was synthesized from methyl 2-(methylsulfanyl)-1-naphthoate through reaction with the di-Grignard reagent derived from 1-bromo-2-(2-bromopropyl)benzene, followed by acid-catalyzed dehydration of the intermediate indanol. Oxidation of rac-3 with m-CPBA gave the diastereomeric sulfoxides (aR*,R S *)-5 and (aR*,S S *)-6, with the relative configuration of 5 established using single-crystal X-ray diffraction. The dichloro[η 5 :κS-indenylsulfanyl and -sulfinyl]rhodium complexes rac-4, (pR*,S S *)-7, and (pR*,R S *)-8 were synthesized through reaction of the ligands rac-3, (aR*,R S *)-5, and (aR*,S S *)-6, respectively, with rhodium trichloride in 9:1 methanol/water solution heated under reflux. The use of water as a cosolvent was found to be critical for obtaining good yields in the complexation reactions. Solid-state structures for the racemic rhodium complexes were determined through single-crystal X-ray diffraction. The enantiomers of the ligands 3, 5, and 6 were obtained in high enantiopurity through subjecting rac-3 to a series of Kagan asymmetric sulfoxidation, deoxygenation, and resulfoxidation reactions. The enantiomeric relationship of the rhodium complexes derived from the enantio-enriched ligands was confirmed by CD spectroscopy, and the high enantiopurity of the complexes established by 1 H NMR analysis using the chiral shift reagent Eu(hfc) 3 . The absolute configurations of the nonracemic ligands and rhodium complexes were established by a singlecrystal X-ray diffraction determination of the solid-state structure of (pS,S S )-8, with the Flack parameter refining to 0.00(2). ■ INTRODUCTIONPlanar chiral ferrocenyl ligands have been successfully utilized in a wide range of asymmetric transition-metal-catalyzed reactions. While the iron center does not participate directly in the catalytic cycle of these reactions, the chemical robustness of ferrocenes has the advantage of enabling numerous synthetic transformations that allow for the introduction of a variety of different coordinating groups, together with specific strategies for the stereoselective creation of the planar chiral element. 1 Planar chiral transition-metal complexes where the metal involved in the planar chiral element is also the site for catalysis have also been examined as asymmetric catalysts. The most successful examples to date are early transition-metal and lanthanide metallocenes, in particular ansa-metallocenes, where a tether between the cyclopentadienyl (Cp; we also use this abbreviation to cover related indenyl and fluorenyl systems) rings prevents the normally facile rotation around the Cp−metal axis, creating a well-defined steric and electronic environment around the metal. 2 As an extension of this development, planar chiral constrainedgeometry half-sandwich metal complexes would appear to be an attractive target for use in asymmetric catalysis. Takahashi and Onitsuka and their co-workers have, for example, demonstrated that planar chiral ruthen...

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“…In particular, using these fragments a number of metallacarboranes [2][3][4][5] and triple-decker complexes [6][7][8] have been prepared. In contrast, chemistry of the related fragment [Cb Ã Pt] 2+ (Cb Ã = g-C 4 Me 4 ) is notably less developed.…”

Section: Introductionmentioning

confidence: 99%

Metallacarboranes and triple-decker complexes with the (C4Me4)Pt fragment

Loginov

Starikova

Petrovskaya

et al. 2009

Journal of Organometallic Chemistry

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Indenyl carbametallaboranes

Cited by 24 publications

References 12 publications

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

Metallacarboranes and triple-decker complexes with the (C4Me4)Pt fragment

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Indenyl carbametallaboranes

Cited by 24 publications

References 12 publications

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

Computational Studies of Structures and Properties of Metallaboranes. 2. Transition-Metal Dicarbollide Complexes

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η5:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

Metallacarboranes and triple-decker complexes with the (C4Me4)Pt fragment

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Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)