Reactions of an Electronically Unsaturated Chromaborane. Coordination of CS2 to (η5-C5Me5)2Cr2B4H8 and Its Hydroboration to a Methanedithiolato Ligand

Hashimoto, Hisako; Shang, Maoyu; Fehlner, Thomas P.

doi:10.1021/om960180e

Cited by 31 publications

(22 citation statements)

References 18 publications

(18 reference statements)

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“…Thus far, only the reaction chemistry of the first example of an unsaturated metallaborane, {Cp*Cr} 2 B 4 H 8 , has been investigated. 44,[54][55][56] The analysis of the bonding in this species is analogous to that of the Mo compound; 57 it lacks two of the prescribed electrons required by its geometry. However, in this case we have no 'normal' transition metal analog with which to compare it and the interpretation of the molecular orbital calculations is not as firmly based.…”

Section: Reaction Chemistrymentioning

confidence: 99%

Exploring the interactions of d-block elements with boron. A case for electronically unsaturated metallaborane clusters

Fehlner¹

1998

J. Chem. Soc., Dalton Trans.

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Section: Reaction Chemistrymentioning

confidence: 99%

Exploring the interactions of d-block elements with boron. A case for electronically unsaturated metallaborane clusters

Fehlner¹

1998

J. Chem. Soc., Dalton Trans.

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“…This may be due to the fact that CS 2 accepts/donates electrons synergistically . Earlier reports on the reactivity of unsaturated [(Cp*Cr) 2 B 4 H 8 ] with CS 2 demonstrate the hydroboration of CS 2 to the methanedithiolato ligand . In general, the insertion or coordination of a heteroatom to the polyhedral borane imparts an electronic effect that ultimately modifies the reactivity of the parent compound .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

et al. 2017

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The quadruply bridged bimetallic dithiolato complex [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] (3) and the open-cage triple-decker complex [(Cp*W) 2 (μ-S)(μ-η 4 :η 4 -B 2 H 2 S 2 )] (2) have been prepared by treatment of CS 2 with in situ generated [(Cp*W) 2 (B 2 H 6 ) 2 ] (1) obtained by the reaction of [Cp*WCl 4 ] with [LiBH 4 ·thf ]. The solid-state X-ray diffraction structures of these complexes show the presence of doubly bridging η 2 -S 2 B 2 H 2 and η 2 -S 2 CH 2 ligands with a short W-W bond. While many dimolybdenumsulfur compounds are known, examples of the tungstendithilato complexes are relatively few, and in this respect, the isolation of [(Cp*W) 2 (μ-S) 2 (μ,η 2 -S 2 CH 2 )] represents a rare exam- [a] 5434 ple of this type. Electronic-structure analysis, on the grounds of density functional theory (DFT), together with X-ray diffraction studies, has rationalized the presence of short W-W and B-B bonds. Large HOMO-LUMO gaps have been observed for both compounds, which is consistent with their thermodynamic stability. All of the compounds have been characterized by mass spectrometry, IR spectroscopy, and 1 H NMR, 11 B NMR, and 13 C NMR spectroscopy in solution, and the structural architectures have been unambiguously established by X-ray diffraction crystallographic analysis. Scheme 1. Structurally characterized dithiolato-bridged binuclear transitionmetal complexes [Mo = CpMo (I-V) and V = CpV (VI)]. [11a,13] Scheme 2. Synthesis of compounds 2, 2a, and 3.

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“…On the basis of the general concern of the electron donating/accepting properties of CS 2 and CO 2 , various binding modes with one or more metal atoms have been recognized [69]. However, reactivities of these ligands towards polyhedral metallaborane clusters have been sparsely explored [70][71][72][73][74]. In this context, Fehlner and colleagues described the reactivity of CS 2 with an unsaturated chromaborane cluster [(Cp*Cr) 2 B 4 H 8 ], which underwent metal-assisted hydroboration and successively converted to a methanedithiolato ligand [71].…”

Section: Introductionmentioning

confidence: 99%

“…However, reactivities of these ligands towards polyhedral metallaborane clusters have been sparsely explored [70][71][72][73][74]. In this context, Fehlner and colleagues described the reactivity of CS 2 with an unsaturated chromaborane cluster [(Cp*Cr) 2 B 4 H 8 ], which underwent metal-assisted hydroboration and successively converted to a methanedithiolato ligand [71]. Following this, our group reported the reaction of CS 2 with nido- [69].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Trithia-Borinane Complexes Stabilized in Diruthenium Core: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BR}] (R = H or SMe)

et al. 2019

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The thermolysis of arachno-1 [(Cp*Ru)2(B3H8)(CS2H)] in the presence of tellurium powder yielded a series of ruthenium trithia-borinane complexes: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BH}] 2, [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3B(SMe)}] 3, and [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BH}] 4. Compounds 2–4 were considered as ruthenium trithia-borinane complexes, where the central six-membered ring {C2BS3} adopted a boat conformation. Compounds 2–4 were similar to our recently reported ruthenium diborinane complex [(Cp*Ru){(η2-SCHS)CH2S2(BH2)2}]. Unlike diborinane, where the central six-membered ring {CB2S3} adopted a chair conformation, compounds 2–4 adopted a boat conformation. In an attempt to convert arachno-1 into a closo or nido cluster, we pyrolyzed it in toluene. Interestingly, the reaction led to the isolation of a capped butterfly cluster, [(Cp*Ru)2(B3H5)(CS2H2)] 5. All the compounds were characterized by 1H, 11B{1H}, and 13C{1H} NMR spectroscopy and mass spectrometry. The molecular structures of complexes 2, 3, and 5 were also determined by single-crystal X-ray diffraction analysis.

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Reactions of an Electronically Unsaturated Chromaborane. Coordination of CS₂ to (η⁵-C₅Me₅)₂Cr₂B₄H₈ and Its Hydroboration to a Methanedithiolato Ligand

Cited by 31 publications

References 18 publications

Exploring the interactions of d-block elements with boron. A case for electronically unsaturated metallaborane clusters

Exploring the interactions of d-block elements with boron. A case for electronically unsaturated metallaborane clusters

Synthesis, Structures, and Characterization of Dimeric Neutral Dithiolato‐Bridged Tungsten Complexes

Synthesis of Trithia-Borinane Complexes Stabilized in Diruthenium Core: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BR}] (R = H or SMe)

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