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]-.

Engineered Anchor Peptide LCI with a Cobalt Cofactor Enhances Oxidation Efficiency of Polystyrene Microparticles.

A typical component of polymer waste is polystyrene (PS) used in numerous applications, but degraded only slowly in the environment due to its hydrophobic properties. To increase the reactivity of polystyrene, polar groups need to be introduced. Here, biohybrid catalysts based on the engineered anchor peptide LCI_F16C are presented, which are capable of attaching to polystyrene microparticles and hydroxylating benzylic C-H bonds in polystyrene microparticles using commercially available oxone as oxidant. LCI peptides achieve a dense surface coverage of PS through monolayer formation within minutes in aqueous solutions at ambient temperature. The catalytically active cobalt cofactor Co-L1 or Co-L2 with a modified NNNN macrocyclic TACD ligand (TACD=1,4,7,10-tetraazacyclododecane) is covalently bound to the anchor peptide LCI through a maleimide linker. Compared to the free cofactors, a 12- to 15-fold improvement in catalytic activity using biohybrid catalysts based on LCI_F16C was observed.

Benzylic C(sp3 )-H Bond Oxidation with Ketone Selectivity by a Cobalt(IV)-Oxo Embedded in a ß-Barrel Protein.

Artificial metalloenzymes have emerged as biohybrid catalysts that allow to combine the reactivity of a metal catalyst with the flexibility of protein scaffolds. This work reports the artificial metalloenzymes based on the ß-barrel protein nitrobindin NB4, in which a cofactor [CoII X(Me3 TACD-Mal)]+ X- (X=Cl, Br; Me3 TACD=N,N' ,N''-trimethyl-1,4,7,10-tetraazacyclododecane, Mal=CH2 CH2 CH2 NC4 H2 O2 ) was covalently anchored via a Michael addition reaction. These biohybrid catalysts showed higher efficiency than the free cobalt complexes for the oxidation of benzylic C(sp3 )-H bonds in aqueous media. Using commercially available oxone (2KHSO5 ⋅ KHSO4 ⋅ K2 SO4 ) as oxidant, a total turnover number of up to 220 and 97 % ketone selectivity were achieved for tetralin. As catalytically active intermediate, a mononuclear terminal cobalt(IV)-oxo species [Co(IV)=O]2+ was generated by reacting the cobalt(II) cofactor with oxone in aqueous solution and characterized by ESI-TOF MS.

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.

Formate complexes of tri- and tetravalent titanium supported by a tris(phenolato)amine ligand.

Titanium(III) and titanium(IV) formate complexes supported by the sterically encumbering tris(phenolato)amine ligand (H3(O3N) = tris(4,6-di-tert-butyl-2-hydroxybenzyl)amine) are described. Salt metathesis of the chlorido precursor [(O3N)TiCl] (1-Cl) with sodium formate in a 2 : 1 ratio in THF gave a dimer of sodium dititanium triformate units with 12-membered ring [Na{(O3N)Ti}2(µ-OCHO-ηO:ηO')3]2 (3-Na) when crystallized from acetonitrile. Complex 3-Na was also prepared by reacting the previously reported terminal formate complex [(O3N)Ti(OCHO)] (2) with excess sodium formate. Salt metathesis of 1-Cl with potassium formate gave a tetratitanium cluster of the composition [K3{(O3N)Ti}4(OCHO)7] (3-K) which can be also obtained by treating 2 with potassium formate. In 3-K both Ti and K centers are six-coordinate. The titanium(III) complexes [(O3N)Ti(L)] (4-L, L = THF, THP, Et2O) and solvent free dimeric [(O3N)Ti]2 (5) were synthesized by reduction of 1-Cl with sodium sand or magnesium in THF, THP, Et2O, and n-pentane, respectively. The tert-butyl formate adduct of titanium(III)-[(O3N)Ti(tBuOCHO)] (6) was isolated by reacting 4-L or 5 with tert-butyl formate. Complex 6 is thermolabile and slowly decomposed in solution to produce a formate-bridged mixed-valence titanium(III)/titanium(IV) complex [{(O3N)Ti}2(µ-OCHO-ηO:ηO')] (7) which further decomposed to a mixture containing 2, [(O3N)Ti(OH)] and [(O3N)Ti-O-Ti(O3N)]. All new complexes were isolated in moderate to good yields and fully characterized by elemental analysis, 1H and 13C NMR spectroscopy, and single crystal X-ray diffraction analysis. For the titanium(III) complexes solution magnetic moments were measured by the Evans method and EPR spectra recorded as toluene glass at 77 K.

Manipulating electron transfer - the influence of substituents on novel copper guanidine quinolinyl complexes.

Copper guanidine quinolinyl complexes act as good entatic state models due to their distorted structures leading to a high similarity between Cu(i) and Cu(ii) complexes. For a better understanding of the entatic state principle regarding electron transfer a series of guanidine quinolinyl ligands with different substituents in the 2- and 4-position were synthesized to examine the influence on the electron transfer properties of the corresponding copper complexes. Substituents with different steric or electronic influences were chosen. The effects on the properties of the copper complexes were studied applying different experimental and theoretical methods. The molecular structures of the bis(chelate) copper complexes were examined in the solid state by single-crystal X-ray diffraction and in solution by X-ray absorption spectroscopy and density functional theory (DFT) calculations revealing a significant impact of the substituents on the complex structures. For a better insight natural bond orbital (NBO) calculations of the ligands and copper complexes were performed. The electron transfer was analysed by the determination of the electron self-exchange rates following Marcus theory. The obtained results were correlated with the results of the structural analysis of the complexes and of the NBO calculations. Nelsen's four-point method calculations give a deeper understanding of the thermodynamic properties of the electron transfer. These studies reveal a significant impact of the substituents on the properties of the copper complexes.

Strontium Hydride Cations Supported by a Large NNNNN Type Macrocycle: Synthesis, Structure, and Hydrofunctionalization Catalysis.

The use of the 15-membered NNNNN macrocyclic ligand Me5PACP (Me5PACP = 1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) allowed the isolation of two cationic strontium hydride complexes by hydrogenolysis of benzyl precursors. Treatment of sparingly soluble [(Me5PACP)Sr(CH2Ph)2] with dihydrogen gave free Me5PACP, toluene, and oligomeric strontium hydride [SrH2]n, while hydrogenolysis in the presence of 1 equiv of the benzyl cation [(Me5PACP)Sr(CH2Ph)][B(C6H3-3,5-Me2)4] enabled isolation of the thermally unstable trihydride cation [(Me5PACP)2Sr2(µ-H)3][B(C6H3-3,5-Me2)4]. When the benzyl cation [(Me5PACP)Sr(CH2Ph)][BAr4]2 (Ar = C6H3-3,5-Me2 or C6H4-4-nBu) was reacted with dihydrogen or n-octylsilane, dihydride complexes [(Me5PACP)2Sr2(µ-H)2][BAr4]2 containing a dinuclear core bridged by two hydride ligands were obtained. The soluble dihydride complex [(Me5PACP)2Sr2(µ-H)2][B(C6H4-4-nBu)4]2 was tested in olefin hydrogenation and hydrosilylation catalysis. Kinetic analyses for [(Me5PACP)2Sr2(µ-H)2]2+ showed lower catalytic activity as compared to that of the isostructural calcium homologue [(Me5PACP)2Ca2(µ-H)2]2+. This is explained by a shift in the monomer-dimer equilibrium which precedes the catalytic cycle.

Formation and Reactivity of a Hexahydridosilicate [SiH6 ]2- Coordinated by a Macrocycle-Supported Strontium Cation.

The cationic benzyl complex [(Me4 TACD)Sr(CH2 Ph)][A] (Me4 TACD=1,4,7,10-tetramethyltetraazacyclododecane; A=B(C6 H3 -3,5-Me2 )4 ) reacted with two equivalents of phenylsilane to give the bridging hexahydridosilicate complex [(Me4 TACD)2 Sr2 (thf)4 (µ-κ3 : κ3 -SiH6 )][A]2 (3 a). Rapid phenyl exchange between phenylsilane molecules is assumed to generate monosilane SiH4 that is trapped by two strontium hydride cations [(Me4 TACD)SrH(thf)x ]+ . Complex 3 a decomposed in THF at room temperature to give the terminal silanide complex [(Me4 TACD)Sr(SiH3 )(thf)2 ][A], with release of H2 . Upon reaction with a weak Brønsted acid, CO2 , and 1,3,5,7-cyclooctatetraene SiH4 was released. The reaction of a 1 : 2 mixture of cationic benzyl and neutral dibenzyl complex with phenylsilane gave the trinuclear silanide complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH3 )2 ][A], while n OctSiH3 led to the trinuclear (n-octyl)pentahydridosilicate complex [(Me4 TACD)3 Sr3 (µ2 -H)3 (µ3 -SiH5 n Oct)][A].

Deaggregation of Zinc Dihydride by Lewis Acids Including Carbon Dioxide in the Presence of Nitrogen Donors.

Thermally sensitive polymeric zinc dihydride [ZnH2]n can conveniently be prepared by the reaction of ZnEt2 with [AlH3(NEt3)]. When reacted with CO2 (1 bar) in the presence of chelating N-donor ligands Ln = N,N,N',N'-tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), N,N,N',N″,N''-pentamethyldiethylenetriamine (PMDTA), and 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane (Me4TACD), insertion into the Zn-H bond readily occurred. Depending on the denticity n, formates [(Ln)Zn(OCHO)2] were isolated and structurally characterized, either as a molecule (Ln = TMEDA, TMPDA, PMDTA) or a charge-separated ion pair [(Ln)Zn(OCHO)][OCHO] (Ln = Me4TACD). The reaction of [ZnH2]n with the mild Lewis acid BPh3 in the presence of chelating N-donor ligands Ln gave a series of hydridotriphenylborates, either as a contact ion pair [(L2)Zn(H)(HBPh3)] (L2 = TMEDA, TMPDA) or a separated ion pair [(Ln)Zn(H)][HBPh3] (Ln = PMDTA, Me4TACD). In the crystal, the contact ion pair [(TMEDA)Zn(H)(HBPh3)] showed a bent Zn-H-B bridge indicative of a delocalized Zn-H-B interaction. In contrast, a linear Zn-H-B bridge for [(TMPDA)Zn(H)(HBPh3)] was observed, suggesting a contact ion pair. In THF solution, both complexes show an exchange with free BPh3 as well as [HBPh3]-. DFT calculations suggest the presence of [HBPh3]- anion with a highly polarized B-H bond that interacts with the Lewis acidic zinc hydride cation [(L2)Zn(H)]+. The hydridotriphenylborates [(Ln)Zn(H)(HBPh3)] underwent CO2 insertion to give (formato)zinc (formoxy)triphenylborate complexes [(Ln)Zn(OCHO)][(OCHO)BPh3] (Ln = TMPDA, PMDTA, Me4TACD). For Ln = TMEDA, a dinuclear complex [(Ln)2Zn2(µ-OCHO)3][(OCHO)BPh3] was isolated. Hydridotriphenylborates [(Ln)Zn(H)(HBPh3)] catalyzed the hydrosilylation of CO2 (1 bar) by nBuMe2SiH in THF at 70 °C to give formoxysilane and (methoxy)silane.

Scandium Reduced Arene Complex: Protonation and Reaction with Azobenzene.

The reactivity of the reduced anthracene complex of scandium [Li(thf)3 ][Sc{N(tBu)Xy}2 (anth)] (2-anth-Li) (Xy=3,5-Me2 C6 H3 ; anth=C14 H10 2- , thf=tetrahydrofuran) toward Brønsted acid [NEt3 H][BPh4 ] and azobenzene is reported. While a stepwise protonation of 2-anth-Li with two equivalents of [NEt3 H][BPh4 ] afforded the scandium cation [Sc{N(tBu)Xy}2 (thf)2 ][BPh4 ] (3), reduction of azobenzene gave a thermolabile, anionic scandium reduced azobenzene complex [Li(thf)][Sc{N(tBu)Xy}2 (η2 -PhNNPh)] (4), which slowly lost one of the anilide ligands to form the neutral scandium azobenzene complex dimer [Sc{N(tBu)Xy}(µ-η2 :η2 -Ph2 N2 )]2 (5). Exposure of 3 to CO2 produced the scandium carbamate complex [Sc{κ2 -O2 CN(tBu)(Xy)}2 ][BPh4 ] (6) as a result of CO2 insertion into the Sc-N bonds. In an attempt to prepare scandium hydrides, the reaction of 3 with the hydride sources LiAlH4 and Na[BEt3 H] led to the terminal aluminum hydride [AlH{N(tBu)Xy}2 (thf)] (7) and the scandium n-butoxide [Sc{N(tBu)(Xy)}2 (µ-OnBu)] (8) after Sc/Al transmetalation and nucleophilic ring-opening of THF, respectively. All reported compounds isolated in moderate to good yields were fully characterized.

Dihydrogen cleavage by a dimetalloxycarbene-borane frustrated Lewis pair.

A frustrated Lewis pair of dititanoxycarbene [(Ti(N[tBu]Ar)3)2(µ-CO2)] (Ar = 3,5-Me2C6H3) and B(C6F5)3 cleaved dihydrogen under ambient conditions to give the zwitterionic formate [(Ti(N[tBu]Ar)3)2(µ-OCHO-ηO:ηO')(B(C6F5)3)] and the hydrido borate [Ti(N[tBu]Ar)3][HB(C6F5)3].

Cationic strontium hydride complexes supported by an NNNN-type macrocycle.

A trinuclear strontium hydride [(Me4TACD)3Sr3(µ2-H)4(thf)][B(C6H3-3,5-Me2)4]2 (Me4TACD = 1,4,7,10-tetramethyltetraazacyclododecane) and a mixed calcium strontium hydride [(Me4TACD)2CaSr(µ-H)2(thf)][B(C6H3-3,5-Me2)4]2 were isolated by hydrogenolysis of cationic benzyl precursors. A solution of [(Me4TACD)2CaSr(µ-H)2(thf)][B(C6H3-3,5-Me2)4]2 shows hydride ligand exchange between calcium and strontium centers and higher affinity of the hydride ligand toward calcium.

Reduced Arene Complexes of Hafnium Supported by a Triamidoamine Ligand.

A series of hafnium complexes with a reduced arene of the general formula [K(L)][Hf(Xy-N3 N)(arene)] (Xy-N3 N={(3,5-Me2 C6 H3 )NCH2 CH2 }3 N3- , L=THF, 18-crown-6; arene=C10 H8 2- , C14 H10 2- ) mimic the chemistry of hafnium in its formal oxidation state +II. All compounds were obtained upon reduction of the chlorido complex [HfCl(Xy-N3 N)(thf)] with two equivalents of potassium naphthalenide or anthracenide. The reducing nature and the basicity of the reduced anthracene ligand were explored in the reaction of benzonitrile and azobenzene, and by deprotonation of tert-butylacetylene, respectively. The reduction of benzonitrile provides an initial double nitrile insertion product under kinetic control that rearranges after extrusion of one of the inserted nitriles to a hafnium imido complex as the thermodynamic product. The reduction of azobenzene resulted in a diphenylhydrazido(2-) complex. Treatment of terminal alkynes with the anthracene or diphenylhydrazido(2-) complex led to the selective protonation of the corresponding dianionic ligand.

Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring-Size Effect of Macrocyclic Ligands on Activity.

The fifteen-membered NNNNN macrocycle Me5 PACP (Me5 PACP=1,4,7,10,13-pentamethyl-1,4,7,10,13-pentaazacyclopentadecane) stabilized the [CaH]+ fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium dibenzyl with the conjugate acid of Me5 PACP followed by hydrogenolysis or treating with n OctSiH3 of the intermediate calcium benzyl cation. The calcium hydride catalyzed the hydrogenation and hydrosilylation of unactivated olefins faster than the analogous calcium complex stabilized by the twelve-membered NNNN macrocycle Me4 TACD (Me4 TACD=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Kinetic investigations indicate that higher catalytic efficiency for the Me5 PACP stabilized calcium hydride is due to easier dissociation of the dimer in solution when compared to the Me4 TACD analogue.

Molecular Zinc Hydride Cations [ZnH]+ : Synthesis, Structure, and CO2 Hydrosilylation Catalysis.

Protonolysis of [ZnH2 ]n with the conjugated Brønsted acid of the bidentate diamine TMEDA (N,N,N',N'-tetramethylethane-1,2-diamine) and TEEDA (N,N,N',N'-tetraethylethane-1,2-diamine) gave the zinc hydride cation [(L2 )ZnH]+ , isolable either as the mononuclear THF adduct [(L2 )ZnH(thf)]+ [BArF 4 ]- (L2 =TMEDA; BArF 4 - =[B(3,5-(CF3 )2 -C6 H3 )4 ]- ) or as the dimer [{(L2 )Zn)}2 (µ-H)2 ]2+ [BArF 4 ]- 2 (L2 =TEEDA). In contrast to [ZnH2 ]n , the cationic zinc hydrides are thermally stable and soluble in THF. [(L2 )ZnH]+ was also shown to form di- and trinuclear adducts of the elusive neutral [(L2 )ZnH2 ]. All hydride-containing cations readily inserted CO2 to give the corresponding formate complexes. [(TMEDA)ZnH]+ [BArF 4 ]- catalyzed the hydrosilylation of CO2 with tertiary hydrosilanes to give stepwise formoxy silane, methyl formate, and methoxy silane. The unexpected formation of methyl formate was shown to result from the zinc-catalyzed transesterification of methoxy silane with formoxy silane, which was eventually converted into methoxy silane as well.

Reactivity of a Molecular Calcium Hydride Cation ([CaH]+) Supported by an NNNN Macrocycle.

The hydride ligand in the cationic calcium hydride supported by a NNNN-type macrocycle, [(Me4TACD)2Ca2(µ-H)2(THF)][BAr4]2 (1; Me4TACD = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; THF = tetrahydrofuran; BAr4 = B(C6H3-3,5-Me2)4), shows, in addition to its Brönsted basicity toward weak acids, a pronounced nucleophilicity resulting in nucleophilic substitution or insertion (addition) at a silicon or sp2 carbon center. Terminal acetylenes RC≡CH (R = SiMe3, cyclopropyl) as well as 1,4-diphenylbutadiene were deprotonated by 1 to give dinuclear complexes [(Me4TACD)2Ca2(µ-C≡CR)2][BAr4]2 (2a, R = SiMe3; 2b, R = cyclopropyl) and [(Me4TACD)2Ca2(µ2-η4-1,4-Ph2C4H2)][BAr4]2 (3) with H2 evolution. The addition reaction with BH3(THF) gave a tetrahydridoborate complex, [(Me4TACD)Ca(BH4)(THF)2][BAr4] (4), with κ2-H2BH2 coordination in the solid state, suggesting a pronounced Lewis acidic calcium center. The behavior resulting from both Lewis acidity and hydricity becomes apparent in the nucleophilic substitution of fluorobenzene by 1 to give benzene and the dimeric fluoride complex [(Me4TACD)2Ca2(µ-F)2(THF)][BAr4]2·2.5THF (5). Analogous nucleophilic substitution reaction is observed for heterofunctionalized organosilanes XSiR3 [X = I, N(SiHMe2)2, N3; R = Me3 or HMe2], which resulted in the formation of calcium complexes [(Me4TACD)Ca(X)(THF)n][BAr4] (6-8) containing an X ligand along with hydrosilane HSiR3. An insertion reaction by 1 was observed with CO2 and CO to give dinuclear formato complex [(Me4TACD)2Ca2(µ-OCHO)2][BAr4]2 (9) and cis-enediolato complex [(Me4TACD)2Ca2(µ-OCH═CHO)][BAr4]2·3.5THF (10), respectively. The latter is believed to have been formed as a result of the dimerization of an initially generated formyl or oxymethylene complex, [(Me4TACD)Ca(OCH)]+.

Reduced Arene Complexes of Scandium.

Alkali metal naphthalenide or anthracenide reacted with scandium(III) anilides [Sc(X){N(tBu)Xy}2 (thf)] (X=N(tBu)Xy (1); X=Cl (2); Xy=C6 H3 -3,5-Me2 ) to give scandium complexes [M(thf)n ][Sc{N(tBu)Xy}2 (RA)] (M=Li-K; n=1-6; RA=C10 H8 2- (3-Naph-K) and C14 H10 2- (3-Anth-M)) containing a reduced arene ligand. Single-crystal X-ray diffraction revealed the scandium(III) center bonded to the naphthalene dianion in a σ2 :π-coordination mode, whereas the anthracene dianion is symmetrically attached to the scandium(III) center in a σ2 -fashion. All compounds have been characterized by multinuclear, including 45 Sc NMR spectroscopy. Quantum chemical calculations of these intensely colored arene complexes confirm scandium to be in the oxidation state +3. The intense absorptions observed in the UV/Vis spectra are due to ligand-to-metal charge transfers. Whereas nitriles underwent C-C coupling reaction with the reduced arene ligand, the reaction with one equivalent of [NEt3 H][BPh4 ] led to the mono-protonation of the reduced arene ligand.

Alkali Metal Triphenyl- and Trihydridosilanides Stabilized by a Macrocyclic Polyamine Ligand.

Potassium silanide [KSiH3 ]∞ contains 4.2 wt % of hydrogen and has been intensely studied as hydrogen storage material. The macrocyclic ligand Me4 TACD (1,4,7,10-tetramethyl-1,4,7,10-tetraaminocyclododecane, L) stabilizes the full range of triphenylsilyl complexes [(L)MSiPh3 ]n (M=Li-Cs), which react with H2 or PhSiH3 to form molecular [(L)MSiH3 ]n that can be isolated in soluble form and fully characterized.

Regioselective Hydrosilylation of Olefins Catalyzed by a Molecular Calcium Hydride Cation.

Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH]+ stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH3 underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.