Silicon Analogues of Cyclopropyl Radical Derived from a Highly Stable Cyclic Disilene Compound Featuring a Si-Br Bond.

A halogen-substituted cyclic disilene compound, bromocyclotrisilene, Si3Br(Eind)3 (3a), bearing fused-ring bulky Eind (a: R1 = R2 = Et) groups, has been synthesized as an extraordinarily air-stable compound by the reduction of 1,2-dibromodisilene, (Eind)BrSi═SiBr(Eind) (2a), or tribromosilane, (Eind)SiBr3 (1a), with the Mg or Li metal. The X-ray diffraction analysis of 3a showed that the disilene moiety has an almost planar, but slightly trans-bent structure. Even though 3a is quite air-stable both in solutions and in the solid state, its Si-Br bond is reactive under reducing conditions. The further treatment of 3a with the Li metal leads to the formation of room-temperature thermally stable silicon homologues of the cyclopropyl radical, i.e., the cyclotrisilanyl radicals (6a) [6a(syn) and 6a(anti)], via intramolecular C-H bond activation in a transient silicon homologue of the cyclopropenyl radical, i.e., the cyclotrisilenyl radical, [Si3(Eind)3]• (5a). The formation mechanism of 6a from 5a is discussed based on the theoretical calculations. The unique structural and electronic properties of these Si3 three-membered ring species incorporating the Eind groups have been experimentally and theoretically investigated.

Synthesis of (µ2,η3-allyl-η5-oxapentadienyl)diiron pentacarbonyl complexes, an unusual reaction product from η4-(vinylketene)Fe(CO)3 complexes: structure and electron density distribution analysis.

The synthesis of a series of ferrocenylvinylketenes as stable η4-[Fe(CO)3] complexes (3a-f) was successfully accomplished through the reaction of η2-[Fe(CO)4] complexes under mild carbonylation conditions. The reactivity of 3a-f under thermal conditions afforded the unexpected formation of a novel family of (µ2,η3-allyl-η5-oxapentadienyl)diiron pentacarbonyl complexes 5a-f proposed to be formed by a sequence metathesis-haptotropic rearrangement between the starting η4-vinylketene iron(0) complex 3 and a η4-vinylcarbene iron(0) complex trapped in situ after a reversible carbonylation process favored by the thermal conditions. An electron density distribution analysis (EDD) of 5e using high-resolution X-ray diffraction data in combination with the DFT framework was performed to understand the electronic communication between the two iron fragments.

Iodine-promoted insertion of the oxygen atom from water in η4-vinylketene[Fe(CO)3] complexes.

Iodine promotes the in situ formation of iron(II) species from η4-vinylketene[Fe(CO)3] (3a-h) as a key intermediate for the synthesis of 2(5H)-furanones (4a-h) by a sequential water-insertion/carbon-oxygen coupling under mild reaction conditions. Compounds 4a-h were obtained in good to excellent yields. A possible reaction pathway was also proposed by DFT calculations. This methodology can be extended to the synthesis of (5H)-pyrrol-2-ones using anilines, with moderate yields and a few limitations.

Incomplete Electrocyclization of a Sterically Hindered 1,4-Diphosphabutadiene.

Butadiene is the simplest neutral acyclic closed-shell π-conjugated system and is typically sufficiently stable enough to avoid electrocyclization to cyclobutene. In contrast, most congeners of butadiene containing heavier elements are easily converted into the corresponding 4-membered cyclobutene system. Herein, we demonstrate that the gauche 1,4-diphosphabutadiene (P=C-C=P) skeleton in a sterically encumbered 2,3-bis(phosphanylidene)-1,4-disilinane can be remarkably perturbed due to "incomplete electrocyclization" where P=C-C=P partially form the corresponding 1,2-dihydrodiphosphete (3,4-diphosphacyclobutene) by [2+2] electrocyclization. 31 P NMR data obtained in solution indicated that the coexistence of a closed ring substantially reduces the open-ring characteristics of the P=C-C=P moiety. However, the 31 P CP-MAS spectrum of 2,3-bis(phosphanylidene)-1,4-disilinane showed that the P=C-C=P structure is predominant in the solid-state. Single-crystal X-ray analysis revealed that decreasing the temperature promoted the generation of small amounts of incomplete 1,2-dihydrodiphosphete system in the crystalline state. Furthermore, the 1,2-dihydrodiphosphete units disappeared upon warming the single crystal, and this unique solid-state electrocyclization reaction was reversible.

Cyclic (Amino)(Phosphonium Bora-Ylide)Silanone: A Remarkable Room-Temperature-Persistent Silanone.

A silanone substituted by bulky amino and phosphonium bora-ylide substituents has been isolated in crystalline form. Thanks to the exceptionally strong electron-donating phosphonium bora-ylide substituent, the lifetime at room temperature of the silanone is dramatically extended (t1/2 =4 days) compared to the related (amino)(phosphonium ylide)silanone VI (t1/2 =5 h), allowing easier manipulation and its use as precursor of new valuable silicon compounds. The interaction of silanone with a weak Lewis acid such as MgBr2 increases further its stability (no degradation after 3 weeks at room temperature).

Exceptionally Strong Electron-Donating Ability of Bora-Ylide Substituent vis-à-vis Silylene and Silylium Ion.

Electropositive boron-based substituent (phosphonium bora-ylide) with an exceptionally strong π- and σ-electron donating character dramatically increases the stability of a new type of N-heterocyclic silylene 2 featuring amino- and bora-ylide-substituents. Moreover, the related silylium ion 4 and transition-metal-silylene complexes, with trigonal-planar geometries around the silicon center, are also well stabilized. Therefore, the N,B-heterocyclic silylene 2 can be used as a strongly electron-donating innocent ligand in coordination chemistry similarly to N-heterocyclic carbenes.

A Fairly Stable Crystalline Silanone.

Silanones 2 substituted by bulky amino- and phosphonium ylide substituents have been synthesized and isolated in crystalline form. Thanks to the steric protection and the strong electron-donating ability of the substituents, silanones 2 are persistent and only slowly dimerizes at room temperature (t1/2 =0.5 or 5 h). Structural and theoretical analysis of 2 indicate a short Si=O bond (1.533 Å) and an enhanced polarization toward the O atom compared to Me2 Si=O owing to the strong π-electron donation from the phosphonium ylide substituent.

The Lightest Element Phosphoranylidene: NHC-Supported Cyclic Borylidene-Phosphorane with Significant B=P Character.

A borylidene-phosphorane, the lightest phosphoranylidene, which is stabilized by an N-heterocyclic carbene ligand, was synthesized and fully characterized. Experimental electron density analysis and DFT calculations indicate an enhanced ylene character (rather than an ylide character) with an exceptionally strong B→P π-back bonding related to the less electronegative boron compared to phosphorus.

An expedient approach to synthesize fluorescent 3-substituted 4H-quinolizin-4-ones via (η(4)-vinylketene)-Fe(CO)3 complexes.

An efficient and practical methodology for the synthesis of 3-substituted 4H-quinolizin-4-ones using (η(4)-vinylketene)-Fe(CO)3 complexes as key intermediates has been developed. The advantage of this transformation lies in the use of simple and readily available starting materials and mild carbonylation conditions. The fluorescent properties of these compounds were determined and the quantum yield was obtained, ranging from 0.04 to 0.36 depending on the substituent.