Reductively disilylated N-heterocycles as versatile organosilicon reagents

Majumdar, Moumita; Sahoo, Padmini

doi:10.1039/d1dt03331j

Cited by 6 publications

(1 citation statement)

References 107 publications

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“…2, The formation of titanium(II) species requires the use of strong reductants (alkali and alkaline-earth metals, NaC 10 H 8 , KC 8 , LiAlH 4 , etc. ), while weaker reducing metals (e.g., Zn, Mn) or organic reagents (e.g., organosilane reductants, benzylamine) are more appropriate for preparing titanium(III) compounds. In particular, the synthesis of titanium(III) tetrahydridoborato complexes by treatment of titanium(IV) halides with the mild reductant LiBH 4 has been known for decades .…”

Section: Introductionmentioning

confidence: 99%

Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands

et al. 2023

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The synthesis, properties, and reactivity of monocyclopentadienyltitanium(III) complexes stabilized by hydridoborato (BH3R)− ligands are reported. The reactions of the titanium(IV) trichlorides [Ti(η5-C5H5–n Me n )Cl3] with excess LiBH3R (R = H, Me) afford dimeric [{Ti(η5-C5H5–n Me n )(BH4)(μ-BH4)}2] (n = 5 (1), 4 (2), 0 (3)) or monomeric [Ti(η5-C5Me5)(BH3Me)2] (4) titanium(III) derivatives. Compound 3 is a thermally unstable oil and decomposes at room temperature forming a mixed-valence TiII/TiIII tetrametallic species [{Ti(η5-C5H5)(BH4)}2{(μ3-B2H6)Ti(η5-C5H5)}2] (5) with dianionic diborane(6) ligands in a rare μ3-κ2:κ2:κ2-B2H6 coordination mode. Density functional theory (DFT) calculations for 5 agree with a triplet ground state with two inner titanium(II) atoms bonded by a single bond and two outer titanium(III) centers. In contrast to 3, the monomeric tetrahydrofuran adduct derivative [Ti(η5-C5H5)(BH4)2(thf)] (6) is a stable solid. Dimeric 1–3 react with 2,6-lutidinium salts (LutH)X (X = BPh4, OSO2CF3) to afford ion pairs, [Ti(η5-C5H5–n Me n )(BH4)L2](BPh4) (L = thf, n = 5 (7), 4 (8), 0 (9); L = py, n = 5 (10)), or molecular aggregates, [{Ti(η5-C5Me5)(BH4)(μ-O2SOCF3)}2] (11) and [{Ti(η5-C5H5–n Me n )(μ-O2SOCF3)2} x ] (n = 5, x = 3 (12); n = 4, x = 4 (13)), via formation of H2 and (Lut)BH3. Diamagnetic titanium(II) derivatives [{Ti(η5-C5Me5)(μ-H)}2{(μ-H)2Al(BH3R)(thf)}2] (R = H (14), Me (15)) were isolated in reactions of complexes 1 and 4 with LiAlH4 in tetrahydrofuran.

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Section: Introductionmentioning

confidence: 99%

Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands

et al. 2023

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Recent Advances in the Chemistry of Germanium(II) Cationic Compounds

Mukherjee,

Khan,

Haldar

et al. 2023

Encyclopedia of Inorganic and Bioinorganic Chemistry

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The syntheses and stabilizations of germanium(II) cationic compounds have been known for long. Contemporary research have been engaged in tailoring the germanium(II) cationic species for applications in small‐molecule activation and catalysis. This article comprises the discussion on the three major types of germanium(II) cationic compounds: (1) germanium(II) monocation or germyliumylidene, (2) bis(germyliumylidene), and (3) germanium(II) dication. Herein, earlier reports on the stabilization of germanium(II) mono‐ and dications have been briefly mentioned. The article includes the latest findings on the stabilization of the germanium(II) cationic species. The major focus of the article has been on discussing how the choice of the supporting ligands becomes the determining factor for tuning the frontier electronics and hence the applicability of the cationic germanium(II) compounds. Examples of bond activation at the ambiphilic germanium(II) monocationic sites and their catalytic applications, element–ligand cooperative bond activations, transition metal‐main group cooperative catalysis, reverse polarization at the germanium(II) cationic site, cooperative interactions between two germanium(II) cationic sites, leading to organic transformations, etc., which are some of the remarkable findings, have been discussed. This overview on the advancements made in this field will provide a background knowledge for further explorations.

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Palladium‐Catalyzed Skeletal Rearrangement of Substituted 2‐Silylaryl Triflates via 1,5‐C−Pd/C−Si Bond Exchange

Hayashi,

Tsuda,

Shintani

2023

Angewandte Chemie

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A palladium‐catalyzed skeletal rearrangement of 2‐(2‐allylarylsilyl)aryl triflates has been developed to give highly fused tetrahydrophenanthrosilole derivatives via unprecedented 1,5‐C−Pd/C−Si bond exchange. The reaction pathways can be switched toward 4‐membered ring‐forming C(sp2)−H alkylation by tuning the reaction conditions to give completely different products, fused dihydrodibenzosilepin derivatives, from the same starting materials. The inspection of the reaction conditions revealed the importance of carboxylates in promoting the C−Pd/C−Si bond exchange.

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Reductively disilylated N-heterocycles as versatile organosilicon reagents

Cited by 6 publications

References 107 publications

Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands

Monocyclopentadienyltitanium(III) Complexes with Hydridoborato Ligands

Recent Advances in the Chemistry of Germanium(II) Cationic Compounds

Palladium‐Catalyzed Skeletal Rearrangement of Substituted 2‐Silylaryl Triflates via 1,5‐C−Pd/C−Si Bond Exchange

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