Iron complexes supported by silyl-NHC chelate ligands: synthesis and use for double hydroboration of nitriles.

Iron complexes bearing new silyl-NHC bidentate ligands were synthesised by treating Fe3(CO)12 with a mixture of N-(hydrosilyl)methyl imidazolium salts and a base. These complexes showed high performance in the catalytic double hydroboration of nitrile with pinacolborane (HBpin) to produce N,N-bis(boryl)amine by a combination of UV irradiation and mild heating (60 °C). The product yields for the hydroboration of aromatic and aliphatic nitriles reached 85%-95% (NMR) using an iron complex (5 mol%). Reducing the loading amount of the iron complex to 0.5 mol% still afforded the products in high yields. An analogous ruthenium complex, which was similarly synthesised using Ru3(CO)12, showed lower activity. Stoichiometric reactions of the iron complex with nitriles afforded Fe(0)-N-silylimine complexes, which may be dormant states in nitrile hydroboration. A catalytic mechanism including Fe(0) N-silylimine species is proposed.

Iridium and rhodium complexes bearing a silyl-bipyridine pincer ligand: synthesis, structures and catalytic activity for C-H borylation of arenes.

Unsaturated 16-electron iridium and rhodium complexes bearing a silyl-bipyridine-based SiNN-pincer ligand (BpySiNN) were synthesised and characterised by X-ray crystallography and NMR spectroscopy. The iridium-BpySiNN complex facilitated the catalytic C(sp2)-H borylation of arenes to give arylboronate esters in high yields (≥93%) under mild conditions (∼40 °C).

Resolving Multi-Path Interference in Compressive Time-of-Flight Depth Imaging with a Multi-Tap Macro-Pixel Computational CMOS Image Sensor.

Multi-path interference causes depth errors in indirect time-of-flight (ToF) cameras. In this paper, resolving multi-path interference caused by surface reflections using a multi-tap macro-pixel computational CMOS image sensor is demonstrated. The imaging area is implemented by an array of macro-pixels composed of four subpixels embodied by a four-tap lateral electric field charge modulator (LEFM). This sensor can simultaneously acquire 16 images for different temporal shutters. This method can reproduce more than 16 images based on compressive sensing with multi-frequency shutters and sub-clock shifting. In simulations, an object was placed 16 m away from the sensor, and the depth of an interference object was varied from 1 to 32 m in 1 m steps. The two reflections were separated in two stages: coarse estimation based on a compressive sensing solver and refinement by a nonlinear search to investigate the potential of our sensor. Relative standard deviation (precision) and relative mean error (accuracy) were evaluated under the influence of photon shot noise. The proposed method was verified using a prototype multi-tap macro-pixel computational CMOS image sensor in single-path and dual-path situations. In the experiment, an acrylic plate was placed 1 m or 2 m and a mirror 9.3 m from the sensor.

Neonicotinoids disrupt aquatic food webs and decrease fishery yields.

Invertebrate declines are widespread in terrestrial ecosystems, and pesticide use is often cited as a causal factor. Here, we report that aquatic systems are threatened by the high toxicity and persistence of neonicotinoid insecticides. These effects cascade to higher trophic levels by altering food web structure and dynamics, affecting higher-level consumers. Using data on zooplankton, water quality, and annual fishery yields of eel and smelt, we show that neonicotinoid application to watersheds since 1993 coincided with an 83% decrease in average zooplankton biomass in spring, causing the smelt harvest to collapse from 240 to 22 tons in Lake Shinji, Shimane Prefecture, Japan. This disruption likely also occurs elsewhere, as neonicotinoids are currently the most widely used class of insecticides globally.

Silyl-pyridine-amine pincer-ligated iridium complexes for catalytic silane deuteration via room temperature C-D bond activation of benzene-d6.

Iridium-hydrido complexes bearing a hemilabile silyl-pyridine-amine pincer ligand were synthesised. They were found to catalyse Si-H deuteration of trialkylsilanes with excess benzene-d6 in 99-94% conversion at room temperature through C-D bond activation and H/D exchange.

Multi-Aperture-Based Probabilistic Noise Reduction of Random Telegraph Signal Noise and Photon Shot Noise in Semi-Photon-Counting Complementary-Metal-Oxide-Semiconductor Image Sensor.

A probabilistic method to remove the random telegraph signal (RTS) noise and to increase the signal level is proposed, and was verified by simulation based on measured real sensor noise. Although semi-photon-counting-level (SPCL) ultra-low noise complementary-metal-oxide-semiconductor (CMOS) image sensors (CISs) with high conversion gain pixels have emerged, they still suffer from huge RTS noise, which is inherent to the CISs. The proposed method utilizes a multi-aperture (MA) camera that is composed of multiple sets of an SPCL CIS and a moderately fast and compact imaging lens to emulate a very fast single lens. Due to the redundancy of the MA camera, the RTS noise is removed by the maximum likelihood estimation where noise characteristics are modeled by the probability density distribution. In the proposed method, the photon shot noise is also relatively reduced because of the averaging effect, where the pixel values of all the multiple apertures are considered. An extremely low-light condition that the maximum number of electrons per aperture was the only 2 e - was simulated. PSNRs of a test image for simple averaging, selective averaging (our previous method), and the proposed method were 11.92 dB, 11.61 dB, and 13.14 dB, respectively. The selective averaging, which can remove RTS noise, was worse than the simple averaging because it ignores the pixels with RTS noise and photon shot noise was less improved. The simulation results showed that the proposed method provided the best noise reduction performance.

Synthesis and characterisation of hydrido molybdenum and tungsten complexes having a hemilabile tridentate Si,Si,O-ligand: observation of stepwise hydrosilylation of a nitrile to form an N-silylimine on the metal centre.

Photoinduced decarbonylation of Cp*M(CO)(3)Me (M = Mo and W, Cp* = η(5)-C(5)Me(5)) in the presence of xantsilH(2) [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)] in pentane gave bis(silyl)hydrido complexes Cp*M(κ(2)Si,Si-xantsil)(CO)(2)(H) (1a: M = Mo and 1b: M = W) through two-fold Si-H oxidative addition and methane elimination. Further irradiation of 1a,b in toluene afforded tridentate xantsil complexes Cp*M(κ(3)Si,Si,O-xantsil)(CO)(H) (2a: M = Mo and 2b: M = W) via CO dissociation. Reactions of complexes 2a,b with nitriles led to stoichiometric hydrosilylation at the C[triple bond, length as m-dash]N triple bond. Thus, reaction of 2a,b with t-BuCN at room temperature afforded N-silyliminoacyl complexes 3a,b, through insertion of a nitrile into the M-Si bond, and the products slowly isomerised to the corresponding N-silylimine complexes 4a,bvia intramolecular hydrogen migration. On the other hand, reaction of 2a,b with PhCN afforded N-silylimine complexes 5a,b directly. The molecular structures of 1a, 3a and 5b were determined by X-ray crystallography, revealing that complex 3a has a 3-centre-2-electron (3c-2e) Mo-Si-H bond.

A layered ionic crystal of polar Li@C(60) superatoms.

If the physical properties of C(60) fullerene molecules can be controlled in C(60) products already in use in various applications, the potential for industrial development will be significant. Encapsulation of a metal atom in the C(60) fullerene molecule is a promising way to control its physical properties. However, the isolation of C(60)-based metallofullerenes has been difficult due to their insolubility. Here, we report the complete isolation and determination of the molecular and crystal structure of polar cationic Li@C(60) metallofullerene. The physical and chemical properties of Li@C(60) cation are compared with those of pristine C(60). It is found that the lithium cation is located at off-centre positions in the C(60)-I(h) cage interior and that the [Li(+)@C(60)] salt has a unique two-dimensional structure. The present method of purification and crystallization of C(60)-based metallofullerenes provides a new C(60) fullerene material that contains a metal atom.

Thermal reaction of a ruthenium bis(silyl) complex having a lutidine-based Si,N,Si ligand: formation of a mu-silyl(mu-silylene) diruthenium complex involving a 3c-2e Ru-Si-C interaction.

Thermal reaction of a bis(silyl) complex Ru{kappa(3)Si,Si,N-2,6-(Me(2)SiCH(2))(2)C(5)H(3)N}(CO)(3) in refluxing toluene gave a dinuclear ruthenium complex Ru(2)(mu-SiMe(2))[(Me(2)SiCH(2))C(5)H(3)N{CH(2)Si(Me)CH(2)}C(5)H(3)N(CH(2)SiMe(3))](CO)(4), which has a 3c-2e Ru-Si-C interaction.

Recombination of an Fe-Si-P linkage to an Fe-P-Si linkage through an isolable intermediate phosphasilaferracyclopropane.

Phosphasilaferracycle [Cp*(CO)Fe{kappa(2)Si,P-SiMe(2)PPh(2)}], prepared upon irradiation of [Cp*(CO)(2)FeSiMe(2)PPh(2)], was converted to [Cp*(CO)(2)FeP(Ph)SiMe(2)Ph] under mild conditions. The unusual recombination of the iron, silicon, and phosphorus cores could be achieved through a sequence of 1,2- and 1,3-group migrations in an FeSiP system.

Group 6 metal complexes with a hemilabile tridentate xantsil ligand and facile insertion of tBuCN into a W-Si bond [xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)].

The synthesis and characterization of tungsten and molybdenum complexes of the xanthene-based bis(silyl) ligand (xantsil) with a kappa3(Si,Si,O) coordination mode are reported, where an insertion of tBuCN into a tungsten-silicon bond leads to formation of an eta2-iminoacyl complex.

Synthesis of a vanadium(III) tris(arylthiolato) complex and its reactions with azide and azo compounds: formation of a sulfenamide complex via cleavage of an azo N=N bond.

The tris(arylthiolate) vanadium(III) complex (1) has been synthesized in good yield. This complex is found to undergo CH activation across a V-S bond in the presence of TMEDA to give a cyclometalated species along with free arylthiol. Complex 1 behaves as a two-electron reductant toward Ad-N(3), yielding an imide complex. Treatment of 1 with azobenzene produces an imide-sulfenamide compound, in which an azo N=N bond cleavage takes place concomitant with formation of a V=N and an S-N bond.

Synthesis and structural characterization of silanethiolato complexes having tert-butyldimethylsilyl and trimethylsilyl groups.

Treatment of cyclotrisilathiane (Me2SiS)3 with 3 equiv. of RLi (R = Me, But) in hexane-Et2O afforded the lithium silanethiolates LiSSiMe2R, and the tmeda adduct [(tmeda)LiSSiMe2But]2 1 (tmeda =N,N,N',N'-tetramethylethylenediamine) was isolated in the case of R = But. Reaction of Fe(CH3CN)2(CF3SO3)2, CoCl2, and [Cu(CH3CN)4](PF6) with 1 gave rise to the silanethiolato complexes M(SSiMe2But)2(tmeda)(M = Fe 2, Co 3), and [Cu(SSiMe2But)]4 4, respectively. Complexes (C5H5)2Ti(SSiMe2R)2(R = Me 5, But 6) and Ni(SSiMe2R)2(dppe)[R = Me 7, But 8; dppe = 1,2-bis(diphenylphosphino)ethane] were prepared from treatments of (C5H5)2TiCl2 and NiCl2(dppe) with the corresponding lithium silanethiolates. Complex 7 readily reacted with (C5H5)TiCl3 to produce the Ti-Ni heterobimetallic compound (C5H5)TiCl(mu-S)2Ni(dppe) 9, in which silicon-sulfur bond cleavage took place. Characterization of all compounds through spectroscopic techniques and elemental analyses are also described. X-Ray structural data for compounds 1 and 3-9 are reported.

Coordination chemistry of silanedithiolato ligands derived from cyclotrisilathiane: synthesis and structures of complexes of iron(II), cobalt(II), palladium(II), copper(I), and silver(I).

The coordination chemistry of chelating silanedithiolato ligands has been investigated on Fe(II), Co(II), Pd(II), Cu(I), and Ag(I). Treatment of M(OAc)(2) (M = Fe, Co, Pd) with cyclotrisilathiane (SSiMe(2))(3) in the presence of Lewis bases resulted in formation of Fe(S(2)SiMe(2))(PMDETA) (1), Fe(S(2)SiMe(2))(Me(3)TACN) (2), Co(S(2)SiMe(2))(PMDETA) (3), and Pd(S(2)SiMe(2))(PEt(3))(2) (4) (PMDETA = N,N,N',N',N' '-pentamethyldiethylenetriamine; Me(3)TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane). The analogous reactions of M(OAc) (M = Cu, Ag) in the presence of PEt(3) gave rise to the dinuclear complexes M(2)[(SSiMe(2))(2)S](PEt(3))(3) [M = Cu (5), Ag (6)]. Complexes were characterized in solution by (1)H, (31)P[(1)H], and (29)Si[(1)H] NMR and in the solid state by single-crystal X-ray diffraction. Mononuclear complexes 1-3 have a four-membered MS(2)Si ring, and these five-coordinate complexes adopt trigonal-bipyramidal (for the PMDETA adducts) or square-pyramidal (for the Me(3)TACN adduct) geometries. In dimer 6, the (SSiMe(2))(2)S(2)(-) silanedithiolato ligand bridges two metal centers, one of which is three-coordinate and the other four-coordinate. The chelating effect of silanedithiolato ligands leads to an increase in the stability of silylated thiolato complexes.

Unusual coordination modes of arylthiolates in Mo(eta(5)-SC(6)H(3)-2,6-(SiMe(3))(2))(eta(7)-SC(6)H(3)-2,6-(SiMe(3))(2)).

Treatment of MoCl(3)(thf)(3) with LiSC(6)H(3)-2,6-(SiMe(3))(2) (LiSAr) resulted in formation of the pi-sandwiched bis-arylthiolato complex, Mo(eta(5)-SC(6)H(3)-2,6-(SiMe(3))(2))(eta(7)-SC(6)H(3)-2,6-(SiMe(3))(2)) (1), while the analogous reaction with LiSC(6)H(3)-2-Ph-6-SiMe(3) afforded the trithiolate complex Mo(SC(6)H(3)-2-Ph-6-SiMe(3))(3) (3). The acetonitrile adduct Mo(SAr)(2)(CH(3)CN)(3) (2) was isolated from the CH(3)CN solution of 1, in which one acetonitrile is coordinated to the metal center in an eta(2)-fashion. Structures of 1, 2, and 3 have been determined by X-ray diffraction.

Synthesis and reactions of triphenylsilanethiolato complexes of manganese(II), iron(II), cobalt(II), and nickel(II).

Reactions of Fe[N(SiMe(3))(2)](2) with 1 and 2 equiv of Ph(3)SiSH in hexane afforded dinuclear silanethiolato complexes, [Fe(N(SiMe(3))(2))(mu-SSiPh(3))](2) (1) and [Fe(SSiPh(3))(mu-SSiPh(3))](2) (2), respectively. Various Lewis bases were readily added to 2, generating mononuclear adducts, Fe(SSiPh(3))(2)(L)(2) [L = CH(3)CN (3a), 4-(t)BuC(5)H(4)N (3b), PEt(3) (3c), (LL) = tmeda (3d)]. From the analogous reactions of M[N(SiMe(3))(2)](2) (M = Mn, Co) and [Ni(NPh(2))(2)](2) with Ph(3)SiSH in the presence of TMEDA, the corresponding silanethiolato complexes, M(SSiPh(3))(2)(tmeda) [M = Mn (4), Co (5), Ni (6)], were isolated. Treatment of 3a with (PPh(4))(2)[MoS(4)] or (NEt(4))(2)[FeCl(4)] resulted in formation of a linear trinuclear Fe-Mo-Fe cluster (PPh(4))(2)[MoS(4)(Fe(SSiPh(3))(2))(2)] (7) or a dinuclear complex (NEt(4))(2)[Fe(2)(SSiPh(3))(2)Cl(4)] (8). On the other hand, the reaction of 3a with [Cu(CH(3)CN)(4)](PF(6)) gave a cyclic tetranuclear copper cluster Cu(4)(SSiPh(3))(4) (9), where silanethiolato ligands were transferred from iron to copper. Silicon-sulfur bond cleavage was found to occur when the cobalt complex 5 was treated with (NBu(4))F in THF, and a cobalt-sulfido cluster Co(6)(mu(3)-S)(8)(PPh(3))(6) (10) was isolated upon addition of PPh(3) to the reaction system. The silanethiolato complexes reported here are expected to serve as convenient precursors for sulfido cluster synthesis.

Palladium dimethylsilanedithiolato complex: a precursor for Ti-Pd and Ti-Pd2 heterometallic complexes.

The silanedithiolato complex Pd(S2SiMe2)(PEt3)2 1 reacted with (C5H5)TiCl3 and TiCl4(thf)2 to produce the heterometallic clusters (C5H5)TiCl(mu-S)2Pd(PEt3)2 2 and TiCl2(S)(mu-S)2Pd2(PEt3)4 3 along with silicon-sulfur bond cleavage, respectively.