Hydrogenolysis of Cationic Half-Sandwich Zinc Complexes Containing a Chelating Amine: Facile Cleavage of Zinc-Carbon Bond by Dihydrogen To Give Zinc Hydride Cations.

Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4F] (2a, Cp* = η3-C5Me5, Ln = N,N,N',N'-tetramethylethylenediamine, TMEDA; 2b, Ln = N,N,N',N'-tetraethylethylenediamine, TEEDA; 2c, Cp* = η1-C5Me5, Ln = N,N,N',N'',N''-pentamethyl-diethylenetriamine, PMDTA; Ar4F = (3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4F] (3a,b, m = 1; 3c, m = 0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4F] (5b). Cation 2b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2c underwent C-H bond activation in acetonitrile to give a dinuclear µ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4F]2 (6c).

Dihydrogen Cleavage by a Zinc-Zinc Bond of a Heteroleptic Dizinc(I) Cation.

Oxidative addition of dihydrogen across a metal-metal bond to form reactive metal hydrides in homogeneous catalysis is known for transition metals but not for zinc(I)-zinc(I) bond as found in Carmona's eponymous dizinconene [Zn2Cp*2] (Cp* = η5-C5Me5). Dihydrogen reacted with the heteroleptic zinc(I)-zinc(I) bonded cation [(L2)Zn-ZnCp*][BAr4F] (L2 = TMEDA, N,N,N',N'-tetramethylethylenediamine, TEEDA, N,N,N',N'-tetraethylethylenediamine; ArF = 3,5-(CF3)2C6H3) under 2 bar at 80 °C to give the zinc(II) hydride cation [(L2)ZnH(thf)][BAr4F] along with zinc metal and Cp*H derived from the intermediate [Cp*ZnH]. DFT calculations show that the cleavage of dihydrogen occurs through a highly unsymmetrical transition state. Mechanistic studies agree with a heterolytic cleavage of dihydrogen as a result of the cationic charge and unsymmetrical ligand coordination. To explore the existence of zinc(I) hydride, thermally unstable hydridotriphenylborate complexes of zinc(I) [(L2)Zn(HBPh3)-ZnCp*] (L2 = TMEDA, TEEDA; TMPDA, N,N,N',N'-tetramethyl-1,3-propylenediamine) have been prepared by salt metathesis and were shown to undergo fast exchange with both BPh3 and [HBPh3]-.

Germylenes Exhibiting Solid-State Emissions that Extend to NIR.

Low-valent main group compounds that fluoresce in the solid-state were previously unknown. To address this, we investigated room-temperature photoluminescence from a series of crystals of germylenes 3-8 in this article; they exhibited emissions nearly reaching the NIR. Germylene carboxylates (3-8) were synthesized by reacting dipyrromethene stabilized germylene pyrrolide (2) with carboxylic acids such as acetic acid, trifluoroacetic acid, benzoic acid, p-cyanobenzoic acid, p-nitrobenzoic acid, and acetylsalicylic acid.

Heterobimetallic Hydrides with a Germanium(II)-Zinc Bond.

In the presence of TMEDA (TMEDA=N,N,N',N'-tetramethylethylenediamine), zinc dihydride reacted with germanium(II) compounds (BDI-H)Ge (1) and [(BDI)Ge][B(3,5-(CF3 )2 C6 H3 )4 ] (3) (BDI-H = HC{(C=CH2 )(CMe)(NAr)2 }, BDI = [HC(CMeNAr)2 ]; Ar = 2,6-i Pr2 C6 H3 ) by formal insertion of the germanium(II) center into the Zn-H bond of polymeric [ZnH2 ]n to give neutral and cationic zincagermane with a H-Ge-Zn-H core [(BDI-H)Ge(H)-(H)Zn(tmeda)] (2) and [(BDI)Ge(H)-(H)Zn(tmeda)][B(3,5-(CF3 )2 C6 H3 )4 ] (4), respectively. Compound 2 eliminated [ZnH2 ] giving diamido germylene 1 at 60 °C. Compound 2 and deuterated analogue 2-d2 exchanged with [ZnH2 ]n and [ZnD2 ]n in the presence of TMEDA to give a mixture of 2 and 2-d2 . Compounds 2 and 4 reacted with carbon dioxide (1 bar) at room temperature to form zincagermane diformate [(BDI-H)Ge(OCHO)-(OCHO)Zn(tmeda)] (5) and formate bridged digermylene [({BDI}Ge)2 (µ-OCHO)]+ [B(C6 H3 (CF3 )2 )4 ] (6) along with zinc formate [(tmeda)Zn(µ-OCHO)3 Zn(tmeda)][B(C6 H3 (CF3 )2 )4 ] (7), respectively. The hydridic nature of the Ge-H and Zn-H bonds in 2 and 4 was probed by reactions with Brönsted and Lewis acids.

Aza-Dipyrrinate Stabilized Compounds with a Low-Valent Main Group Element.

The possibility of using aza-dipyrromethene (a-DPM) ligands to stabilize compounds containing low-valent main group elements is demonstrated through the isolation of germylenes, a-DPM(p-tol)GeCl (2), a-DPM(Naph)GeCl (6), and a-DPM(Naph)GeN(TMS)2 (7) (tol=tolyl, Naph=naphthyl). Because of the presence of the a-DPM ligand, these germylenes exhibit an absorption maximum at around 640 nm, a highly red-shifted value previously unknown for germylenes.

Hydroboration and Deoxygenation of CO2 Mediated by a Gallium(I) Cation.

Hydroboration of CO2 to formoxy borane occurs under ambient conditions in acetonitrile using pinacolborane HBpin in the presence of gallium(I) cation [(Me4TACD)Ga][BAr4] (1; Me4TACD = N,N',N″,N'''-tetramethyl-1,4,7,10-tetraazacyclododecane; Ar = C6H3-3,5-Me2). Slow turnover was accompanied by side reactions including ligand scrambling of HBpin to give BH3(CH3CN) and crystalline B2pin3. When 1 was reacted with CO2 alone, the formation of the gallium(III) carbonato complex [(Me4TACD)Ga(κ2-O2CO)][BAr4] (3) along with CO was observed. This complex was assumed to form via the unstable oxido cation [(Me4TACD)Ga=O]+ (4). Reaction of 1 with N2O in the presence of BPh3 confirmed the formation of the oxido cation, which was spectroscopically characterized as a triphenylborane adduct [(Me4TACD)Ga=O(BPh3)][BAr4] (4·BPh3). CO was also detected when CO2 was reacted with 1 in the presence of HBpin, suggesting that compound 3 may also be formed in initial stages of catalysis. Compound 3 reacts with HBpin to give formoxy borane, borane redistribution products, and an unidentified Me4TACD-containing species 5, which was also observed in "catalytic" runs starting from 1, HBpin, and CO2. Hydroboration of CO2 using HBpin with slow turnover and competitive ligand scrambling was also observed in the presence of gallium(III) hydride dication [(Me4TACD)GaH][BAr4]2 (2), which is unreactive toward CO2 in the absence of HBpin.

Air and water stable germacarbonyl compounds.

Germacarbonyl compounds are the germanium analogs of carbonyl compounds requiring an inert atmosphere for stability. Making these compounds survive the ambient conditions was not feasible given the lability of the Ge[double bond, length as m-dash]E bonds (E = O, S, Se, Te). However, the first examples of germacarbonyl compounds synthesized under ambient conditions by taking advantage of dipyrromethene ligand stabilization are detailed here; the isolated compounds are thiogermanone 3, selenogermanone 4, thiogermacarboxylic acid 6, selenogermacarboxylic acid 7, thiogermaester 9, selenogermaester 10, thiogermaamide 12, and selenogermaamide 13 with Ge[double bond, length as m-dash]E bonds (E = S, Se). Compounds 12 and 13 can react under atmospheric conditions with copper(i) halides offering air and water stable monomeric 14-15 and dimeric 16-19 copper(i) complexes (halide = Cl, Br, I). Apart from just binding, selectivity was also observed; thiogermaamide 12 and selenogermaamide 13 bind CuCl and CuBr, respectively, when treated with a mixture of copper(i) halides.

Iridium-Triggered Allylcarbamate Uncaging in Living Cells.

Designing a metal catalyst that addresses the major issues of solubility, stability, toxicity, cell uptake, and reactivity within complex biological milieu for bioorthogonal controlled transformation reactions is a highly formidable challenge. Herein, we report an organoiridium complex that is nontoxic and capable of the uncaging of allyloxycarbonyl-protected amines under biologically relevant conditions and within living cells. The potential applications of this uncaging chemistry have been demonstrated by the generation of diagnostic and therapeutic agents upon the activation of profluorophore and prodrug in a controlled fashion within HeLa cells, providing a valuable tool for numerous potential biological and therapeutic applications.

A Prelude to Biogermylene Chemistry*.

The biological applications of germylenes remain unrealised owing to their unstable nature. We report the isolation of air-, water-, and culture-medium-stable germylene DPMGeOH (3; DPM=dipyrromethene ligand) and its potential biological application. Compound 3 exhibits antiproliferative effects comparable to that of cisplatin in human cancer cells. The cytotoxicity of compound 3 on normal epithelial cells is minimal and is similar to that of the currently used anticancer drugs. These findings provide a framework for a plethora of biological studies using germylenes and have important implications for low-valent main-group chemistry.

Germylene stabilized group 12 metal complexes and their reactivity with chalcogens.

This manuscript reports the first examples of germylene stabilized cadmium complexes {[{(i-Bu)2ATIGe(i-Pr)}2(CdI2)] (3, monomeric), [{(i-Bu)2ATIGe(i-Pr)(CdCl2)}2] (6, dimeric), [{(i-Bu)2ATIGe(i-Pr)(CdI2)}2] (7, dimeric)} and novel germylene zinc complexes {[{(i-Bu)2ATIGe(i-Pr)}2(ZnCl2)] (2, monomeric), [{(i-Bu)2ATIGe(i-Pr)(ZnI2)}2] (5, dimeric)} (ATI = aminotroponiminate). The reactions of germylene zinc complex [{(i-Bu)2ATIGe(i-Pr)(ZnCl2)}2] (4) with elemental sulphur and selenium resulted in the first examples of germathione and germaselenone stabilized ZnCl2 complexes [{(i-Bu)2ATIGe(i-Pr)(S)(ZnCl2)}2] (8) and [{(i-Bu)2ATIGe(i-Pr)(Se)(ZnCl2)}2] (9), respectively. Compound 4 was obtained through the reaction of compound 2 with ZnCl2. Interconversions between the monomeric and dimeric zinc/cadmium complexes (2 ↔ 4/3 ↔ 7) are shown. Compounds 2-3 and 5-9 are characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction studies are performed on compounds 2-3, 5-7, and 9. To understand the nature of bonding in the first examples of germylene cadmium complexes, ab initio calculations are also carried out on compounds 3 and 7.

Donor-acceptor-stabilised germanium analogues of acid chloride, ester, and acyl pyrrole compounds: synthesis and reactivity.

Germaacid chloride, germaester, and N-germaacyl pyrrole compounds were not known previously. Therefore, donor-acceptor-stabilised germaacid chloride (i-Bu)2ATIGe(O)(Cl) → B(C6F5)3 (1), germaester (i-Bu)2ATIGe(O)(OSiPh3) → B(C6F5)3 (2), and N-germaacyl pyrrole (i-Bu)2ATIGe(O)(NC4H4) → B(C6F5)3 (3) compounds, with Cl-Ge[double bond, length as m-dash]O, Ph3SiO-Ge[double bond, length as m-dash]O, and C4H4N-Ge[double bond, length as m-dash]O moieties, respectively, are reported here. Germaacid chloride 1 reacts with PhCCLi, KOt-Bu, and RLi (R = Ph, Me) to afford donor-acceptor-stabilised germaynone (i-Bu)2ATIGe(O)(CCPh) → B(C6F5)3 (4), germaester (i-Bu)2ATIGe(O)(Ot-Bu) → B(C6F5)3 (5), and germanone (i-Bu)2ATIGe(O)(R) → B(C6F5)3 (R = Ph 6, Me 7) compounds, respectively. Interconversion between a germaester and a germaacid chloride is achieved; reaction of germaesters 2 and 5 with TMSCl gave germaacid chloride 1, and 1 reacted with Ph3SiOLi and KOt-Bu to produce germaesters 2 and 5. Reaction of N-germaacyl pyrrole 3 with thiophenol produced a donor-acceptor-stabilised germaacyl thioester (i-Bu)2ATIGe(O)(SPh) → B(C6F5)3 (10). Furthermore, the attempted syntheses of germaamides and germacarboxylic acids are also discussed.

Ge(ii) cation catalyzed hydroboration of aldehydes and ketones.

Well-defined germylene cations [(i-Bu)2ATI]GeOTf (4) and [(i-Bu)2ATIGe][GaCl4] (5) are isolated, and the catalytic utility of compound 4 for the hydroboration of a variety of aldehydes and ketones is reported (ATI = aminotroponiminate).

Expanding the limits of catalysts with low-valent main-group elements for the hydroboration of aldehydes and ketones using [L†Sn(ii)][OTf] (L† = aminotroponate; OTf = triflate).

A triflatostannylene [L†Sn(ii)][OTf] (2) is reported here as an efficient catalyst with low-valent main-group element for the hydroboration of aldehydes and ketones (L† = aminotroponate). Using 0.025-0.25 mol% of compound 2, hydroboration of various aldehydes and ketones is accomplished in 0.13-1.25 h at room temperature; the aliphatic aldehydes show an impressive TOF of around 30 000 h-1. DFT calculations are performed to explore the mechanistic aspects of this reaction suggesting that the reaction proceeds via a stepwise pathway with hydridostannylene [L†Sn(ii)H] (2a) as the active catalyst and the H atom transfer from the Sn-H bond to the carbonyl carbon being the rate determining step.

Catalytic cyanosilylation using germylene stabilized platinum(ii) dicyanide.

The ability of a platinum compound to act as a catalyst for the cyanosilylation of carbonyl compounds is demonstrated through a well-defined germylene stabilized Pt(ii) dicyanide, trans-{(iBu)2ATIGe(iPr)}2Pt(CN)2.