Reactions of (mesityl)n(methyl)2-nsilylene complexes with pyridine-N-oxide (n = 1 and 0): formation of silanone complexes and a disiloxanyloxy complex.

Silanones (OSiR2), a heavier congener of ketones (R2CO), are highly reactive species that are readily converted to oligomeric siloxane (O-SiR2)n. Coordination of silanones to the transition-metal fragments to afford silanone-coordinated complexes is a reliable silanone stabilization method. Recently, our group reported the synthesis, structures, and reactivity of dimesityl-substituted silanone complexes Cp*(OC)2M{OSiMes2(L)}(SiMe3) (M = W, Mo, L: Lewis base, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2). Herein, to investigate the effect of substituents on the silicon atom during the formation of a silanone complex, we demonstrated the use of Mes and smaller Me groups. As a result, the formation of Mes(Me)-substituted silanone molybdenum complex Cp*(OC)2Mo{OSiMes(Me)(py)}(SiMe3) (5b, py: pyridine) was suggested, the silanone tungsten complex Cp*(OC)2W{OSiMes(Me)(DMAP)}(SiMe3) (4a, DMAP: 4-(dimethylamino)pyridine) was obtained, and a dimethyl-substituted disiloxanyloxy(dioxo) complex Cp*(O)2W(OSiMe2OSiMe3) (9) was formed. The reaction of 4a with PMe3 proceeded via the elimination of DMAP and migration of the SiMe3 group to the oxygen atom of the silanone ligand to afford Cp*(OC)2W(SiMes(Me)OSiMe3)(PMe3) (11a). The Mo complex Cp*(OC)2Mo(SiMes(Me)OSiMe3)(PMe3) (11b) was produced by the reaction of Cp*(OC)2Mo{SiMes(Me)}(SiMe3) (7b) with pyridine-N-oxide in the presence of PMe3.

Synthesis and structure of a pyridine-stabilized silanone molybdenum complex and its reactions with PMe3 and acetone.

Silanones (OSiR2) are highly reactive species that readily convert to oligomeric siloxane (O-SiR2)n. The coordination of silanones to transition metal fragments to afford silanone-coordinated complexes is a reliable silanone stabilization method. Herein, a pyridine-stabilized silanone molybdenum complex Cp*(OC)2Mo{OSiMes2(py)}(SiMe3) (2b, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2, and py: pyridine) was synthesized by reacting the silyl(silylene) complex Cp*(OC)2Mo(SiMes2)(SiMe3) (4b) with pyridine-N-oxide in pyridine. X-ray crystal structure analysis revealed that the geometry of complex 2b is similar to those of the previously synthesized DMAP-stabilized analogue Cp*(OC)2Mo{OSiMes2(DMAP)}(SiMe3) (2a, DMAP: 4-(dimethylamino)pyridine). The SiO and Mo-O bond distances in 2b are similar to those observed in 2a, but the N-Si coordination bond of 2b is slightly longer (approximately 0.05 Å) than that of 2a, indicating weaker pyridine coordination than that of DMAP. The reaction of 2a with excess PMe3 in C6D6 at room temperature for 28 h afforded Cp*(OC)2Mo(PMe3)(SiMe3) (5c) in a 43% NMR yield. In contrast, reacting 2b with excess PMe3 in C6D6 at room temperature for 9 h afforded 5c and the five-membered metallacyclic carbene complex Cp*(OC)Mo(C(SiMe3)OSiMes2O)(PMe3) (6) in 10% and 41% NMR yields, respectively. The reactions of pyridine-stabilized silanone complexes Cp*(OC)2M(OSiMes2(py))(SiMe3) (M = Mo (2b) and W (1b)) with acetone proceeded via pyridine elimination, coordination of acetone to the Si center in the silanone ligand, and elimination of HSiMe3 to give Cp*(OC)2M{OSiMes2OC(Me)CH2} (M = Mo (8) and W (9)) in high yields.

2,2,6,6-Tetramethylpiperidine-1-oxyl acts as a volatile inhibitor of ferroptosis and neurological injury.

Ferroptosis, a type of oxidative stress cell death, has been implicated in cell injury in several diseases, and treatments with specific inhibitors have been shown to protect cells and tissues. Here we demonstrated that a treatment with the nitroxide radical, 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), prevented the ferroptotic cell death in an airborne manner. Other TEMPO derivatives and lipophilic antioxidants, such as Trolox and ferrostatin-1, also prevented cell death induced by erastin and RSL3; however, only TEMPO exhibited inhibitory activity from a physically distant location. TEMPO vaporized without decomposing and then dissolved again into a nearby water solution. Volatilized TEMPO inhibited glutamate-induced cell death in mouse hippocampal cell lines and also reduced neuronal cell death in a mouse ischemia model. These results suggest that TEMPO is a unique cell protective agent that acts in a volatility-mediated manner.

Near-Infrared Emitting Ir(III) Complexes Bearing a Dipyrromethene Ligand for Oxygen Imaging of Deeper Tissues In Vivo.

Phosphorescence lifetime imaging microscopy (PLIM) using a phosphorescent oxygen probe is an innovative technique for elucidating the behavior of oxygen in living tissues. In this study, we designed and synthesized an Ir(III) complex, PPYDM-BBMD, that exhibits long-lived phosphorescence in the near-infrared region and enables in vivo oxygen imaging in deeper tissues. PPYDM-BBMD has a π-extended ligand based on a meso-mesityl dipyrromethene structure and phenylpyridine ligands with cationic dimethylamino groups to promote intracellular uptake. This complex gave a phosphorescence spectrum with a maximum at 773 nm in the wavelength range of the so-called biological window and exhibited an exceptionally long lifetime (18.5 µs in degassed acetonitrile), allowing for excellent oxygen sensitivity even in the near-infrared window. PPYDM-BBMD showed a high intracellular uptake in cultured cells and mainly accumulated in the endoplasmic reticulum. We evaluated the oxygen sensitivity of PPYDM-BBMD phosphorescence in alpha mouse liver 12 (AML12) cells based on the Stern-Volmer analysis, which gave an O2-induced quenching rate constant of 1.42 × 103 mmHg-1 s-1. PPYDM-BBMD was administered in the tail veins of anesthetized mice, and confocal one-photon PLIM images of hepatic tissues were measured at different depths from the liver surfaces. The PLIM images visualized the oxygen gradients in hepatic lobules up to a depth of about 100 µm from the liver surfaces with a cellular-level resolution, allowing for the quantification of oxygen partial pressure based on calibration results using AML12 cells.

C-O and C-C bond cleavage of α,ß-unsaturated esters with the assistance of a gallane(pyridyl)iron complex.

Selective fragmentation of α,ß-unsaturated esters into CC, CO, and OR fragments was investigated with the assistance of a gallane(pyridyl)iron complex Cp*(OC)Fe{(η1-HGaMes2)(η1-2-C5H4N)} (1, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2). The reaction of 1 with methyl acrylate in C7D8 afforded vinyliron complex Cp*(OC)2Fe(CHCH2) (2) and 4-membered Ga2O2 cyclic gallane [Mes2GaOMe]2 (3). The C-O and C-C bonds in t-butyl acrylate were cleaved by the reaction with complex 1, producing complex 2 and pyridine-coordinated gallane Mes2(t-BuO)Ga(pyridine) (4). The selective bond cleavage reactions proceeded by the reactions of 1 with methyl methacrylate and methyl 2-butenoate to afford Cp*(OC)2Fe(CR1CHR2) (R1 = Me, R2 = H (5), R1 = H, R2 = Me (6)) and 3. In contrast, compound 3 was formed in 11% NMR yield by the reaction of 1 with methyl 3-butenoate (ß,γ-unsaturated ester), and complex mixtures of unidentified products were obtained by the reaction of 1 with methyl 4-pentenoate (γ,δ-unsaturated ester) and methyl propionate (saturated ester). The treatment of a cyclic ester, α-methylene-γ-butyrolactone, with 1 afforded a 4-membered Ga2O2 cyclic gallane dimer with Cp*(OC)2FeC(CH2)CH2CH2 substituents on the oxygen atoms, namely [Cp*(OC)2FeC(CH2)CH2CH2OGaMes2]2 (7). In addition, the bond cleavage reaction occurred by the reaction of 1 with allyl methyl ether to afford the (η3-allyl)iron complex Cp*(OC)Fe(η3-CH2CHCH2) (8) and 3. These results indicate that the existence of the -CC-C-OR fragment, regardless of the presence or absence of the CO group between the CC and OR fragments, is essential for the bond cleavage reaction.

Synthesis, structure, and reactivity of a pyridine-stabilized silanonetungsten complex.

A pyridine-stabilized silanonetungsten complex Cp*(OC)2W{O[double bond, length as m-dash]SiMes2(py)}(SiMe3) (1b, Cp* = η5-C5Me5, Mes = 2,4,6-Me3C6H2, py = C5H5N) was obtained by the reaction of a silyl(silylene) complex Cp*(OC)2W([double bond, length as m-dash]SiMes2)(SiMe3) (3) with pyridine-N-oxide in pyridine. X-ray crystal structure determination revealed that complex 1b shows a similar geometry to that observed for a previously synthesized DMAP-stabilized analogue, Cp*(OC)2W{O[double bond, length as m-dash]SiMes2(DMAP)}(SiMe3) (1a, DMAP = 4-NMe2C6H4N). The Si[double bond, length as m-dash]O and W-O bond distances in 1b are comparable to those observed in 1a, but the nitrogen to silicon coordination bond of 1b is slightly longer (ca. 0.05 Å) than that of 1a, indicating the weaker coordination of pyridine than that of DMAP. The reaction of 1b with excess PMe3 in C6D6 at r. t. proceeded via elimination of pyridine to afford a five-membered metallacyclic carbene complex, Cp*(OC)W([double bond, length as m-dash]C(SiMe3)OSiMes2O)(PMe3) (5), but that of 1a with PMe3 did not proceed at all. Complex 5 was further transformed in C7D8 at 100 °C for 4 h to give a four-membered W-O-Si-O metallacyclic complex with carbyne and PMe3 ligands, Cp*W(OSiMes2O)([triple bond, length as m-dash]CSiMe3)(PMe3) (7). The structural features of complexes 1b, 5, and 7 are comparable to those suggested theoretically as intermediates in the reaction of 3 with a sulfuration reagent to afford a six-membered metallacyclic carbene complex, Cp*W(S){[double bond, length as m-dash]C(SiMe3)C([double bond, length as m-dash]O)OSiMes2S} (6), indicating that complex 1b and the theoretically proposed silanethione complex are transformed via a similar reaction pathway.

Synthesis, structures, and reactivity of the base-stabilized silanone molybdenum complexes.

Base-stabilized silanone molybdenum complexes were synthesized by the oxygenation of the M=Si bond in the silyl(silylene)molybdenum complex with 1 eq. of PNO in the presence of Lewis base L. The PNO-coordinated silanone complex (L = PNO) was converted to cis-[Cp*(OC)2Mo{OSiMes2(OSiMe3)}(PMe3)] in the presence of excess PMe3.

Ultrasound-induced emission enhancement based on structure-dependent homo- and heterochiral aggregations of chiral binuclear platinum complexes.

Instant and precise control of phosphorescent emission can be performed by ultrasound-induced gelation of organic liquids with chiral, clothespin-shaped trans-bis(salicylaldiminato)Pt(II) complexes, anti-1. Nonemissive solutions of racemic, short-linked anti-1a (n = 5) and optically pure, long-linked anti-1c (n = 7) in organic liquids are transformed immediately into stable phosphorescent gels upon brief irradiation of low-power ultrasound. Emission from the gels can be controlled by sonication time, linker length, and optical activity of the complexes. Several experimental results indicated that structure-dependent homo- and heterochiral aggregations and ultrasound-control of the aggregate morphology are key factors for emission enhancement.

Synthesis of a base-stabilized silanone-coordinated complex by oxygenation of a (silyl)(silylene)tungsten complex.

Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.

Rhodium-catalyzed approach to Mannich-type products using aldimine, alpha,beta-unsaturated ester, and hydrosilane.

A rhodium-catalyzed method for the synthesis of beta-amino esters was accomplished in a one-pot procedure from aldimine, alpha,beta-unsaturated ester and hydrosilane.