One electron reduction transforms high-valent low-spin cobalt alkylidene into high-spin cobalt(ii) carbene radical.

One electron reduction of formally CoIV(OR)2(CPh2) forms the [CoII(OR)2(CPh2)]- anion. Whereas low-spin Co(OR)2([double bond, length as m-dash]CPh2) demonstrated significant alkylidene character, the high-spin [Co(OR)2(CPh2)]- anion features a rare Co(ii)-carbene radical. Treatment of [Co(OR)2(CPh2)][CoCp*2] with xylyl isocyanide triggers formation of two new C-C bonds, and is likely mediated by nucleophilic attack of deprotonated CoCp*2+ on a transient ketenimine.

Superlinearity, saturation, and the PMT-Tailoring and calibration methodology for prompt radiation detectors.

This work illustrates predominant measureable nonlinearities in photomultiplier tubes (PMTs) and introduces a controllable one called "Superlinearity," signifying both a positive nonlinear response and the ability to extend linear operation by counteracting gain saturation mechanisms - charge depletion, space-charge field limitation, and secondary emission surface effects. Recognizing superlinearity and its effect on the temporal step response leads to a true definition of linearity, free of a small-signal linear assumption. Furthermore, given the prevalent use of glass microchannel-plate (MCP) PMTs in favor of a faster impulse response in spite of a small charge limit, we are motivated to examine their nonlinear amplitude response and deploy tailored gain bias string methods to fully harness the maximum linear gain as is usually done for transmissive metal mesh and reflective metal dynode PMTs.

Synthesis and Characterization of a Stable High-Valent Cobalt Carbene Complex.

The formally Co(IV) carbene Co(OR)2(═CPh2) is formed upon the reaction of diphenyldiazomethane with the cobalt bis(alkoxide) precursor Co(OR)2(THF)2. Structural, spectroscopic, and theoretical studies demonstrate that Co(OR)2(═CPh2) has significant high-valent Co(IV)═CPh2 character with non-negligible spin density on the carbene moiety.

Synthesis and Reactions of 3d Metal Complexes with the Bulky Alkoxide Ligand [OC(t)Bu2Ph].

Treatment of NiCl2(dme) and NiBr2(dme) (dme = dimethoxyethane) with 2 equiv of LiOR (OR = OC(t)Bu2Ph) forms the distorted trigonal planar complexes [NiLiX(OR)2(THF)2] (THF = tetrahydrofuran) 5 (X = Cl) and 6 (X = Br). The reaction of CuX2 (X = Cl, Br) with 2 equiv of LiOR affords the Cu(I) product Cu4(OR)4 (7). The same product can be obtained using the Cu(I) starting material CuCl.

Reductive coupling of azides mediated by an iron(II) bis(alkoxide) complex.

The iron(III) hexazene complex (RO)2Fe(μ-κ(2):κ(2)-AdN6Ad)Fe(OR)2 (3) was synthesized via reductive coupling of 1-azidoadamantane at the iron(II) bis(alkoxide) complex Fe(OR)2(THF)2 (2). The X-ray crystal structure depicts electron delocalization within the hexazene moiety. Density functional theory studies propose the formation of an iron azide dimer on the route to hexazene, in which each azide is monoreduced and the iron centers are oxidized to the 3+ oxidation state.