Suppressed aggregation: The unprecedented alumoxane hydrogensulfide [{LAl(SH)}2(μ-O)] and the unique sulfide-bridged compound [{LAl(SH)}2(μ-S)] can be prepared from easily accessible aluminum dihydride [LAlH2] (L=HC[(CMe)N(2,4,6-Me3C6H2)]2−). Owing to cis conformation of terminal SH groups, these compounds represent ideal precursors for synthesis heterometallic compounds.

Equimolar and excess ratio reactions of AlMe(3) Al(i)Bu(3) with the ligands 4,5-(P(E)Ph(2))(2)tzH (tz = 1,2,3-triazole; E O (1), S (2), Se(3)) were performed, showing a vast variety coordination modes. The products obtained, [AlR(2){kappa(2)-O,O'-[4,5-(P(O)Ph(2))(2)tz]}] (R Me (4), (i)Bu (5)), [AlR(2){kappa(3)-N,N',S-[4,5-(P(S)Ph(2))(2)tz]}(mu-tz)](2) (6), R (7)), [AlMe(2){kappa(2)-N,Se-[4,5-(P(Se)Ph(2))(2)tz]}] (8), [Al{kappa(2)-N,Se-[4,5-(P(Se)Ph(2))(2)tz]}(3)] (9),...

The preparation of novel alkali metal chalcogenides supported by multidentate nitrogen rich ligands is reported. Treatment the ligand precursors [H{(4,5-(P(E)Ph(2))(2)tz}] (E = S (1a), Se (1b)) with organolithium reagents or elemental sodium and potassium in tetrahydrofuran (THF) leads to isolation 2-7 high yields. These compounds were characterized analysis, IR spectroscopy, mass spectrometry, solution solid-state multinuclear NMR single crystal X-ray diffraction analysis. In solid state,...

The cyclic alumosiloxane [{LAl(μ-O)(Ph2Si)(μ-O)}2] (3) and alumosilicate [{LAl(μ-O){(tBuO)2Si}(μ-O)}2] (4) were obtained by reaction of the appropriate R2Si(OH)2 precursor (R = Ph, OtBu) with [{LAl(H)}2(μ-O)] (1), providing a nice illustration Loewenstein rule at work molecular level.

Syntheses of the heavy chalcogen-containing alumoxanes [(Me)LAl(SeH)]2(μ-O) (4) and ((Me)LAl)2(μ-Te)(μ-O) (7) were accomplished by reaction ((Me)LAlH)2(μ-O) (2; (Me)L = HC[(CMe)N(2,4,6-Me3C6H2)]2(-)) with either red selenium or metallic tellurium. The aluminum hydrogenselenide [(Me)LAl(SeH)]2(μ-Se) (3) was also prepared from (Me)LAlH2 (1). All compounds characterized spectroscopic methods X-ray diffraction studies. Density functional theory calculations performed on 4 7.

Carbon dioxide is readily fixed when reacting with either alumoxane dihydride [{MeLAl(H)}2(μ-O)] (1) or aluminum [MeLAlH2] (2) (MeL = HC[(CMe)N(2,4,6-Me3C6H2)]2-) to produce bimetallic formates [(MeLAl)2(μ-OCHO)2(μ-O)] (3) and [(MeLAl)2(μ-OCHO)2(μ-H)2] (5), respectively. Furthermore, [(MeLAl)2(μ-OCHO)2(μ-OH)2] (4) easily obtained upon the reaction of 3 5 H2O. The stability unusual dialuminum diformate core observed in stems from proximity Al centers allowing formation two Al-HAl bridges...

Abstract The alkaline 1‐phenyl‐1H‐1, 2, 3, 4‐tetrazole‐5‐thiolate salts, M[C 6 H 5 N 4 CS] (M = Li ( 1 ), Na 2 K 3 Rb ) and Cs )) were obtained characterized by means of mass spectrometry (FAB + NMR H; 13 C) spectroscopy. structures compounds determined X‐ray diffraction methods. ligand shows a rich variety coordination patterns with the cations. formation four‐membered ring MSCN in heavier alkali cations (K, Cs) is shown. In all number around it increases ionic radius. Compounds exhibited...

The 4,5-bis(diphenylphosphoranyl)-1,2,3-triazole [4,5-(P(E)Ph2)2tz] derivatives of indium {kappa3-N,N',E-[4,5-(P(E)Ph2)2(mu-tz)]InMe2}2 (E = O2, S3, Se4) were prepared in good yield. In addition, compound 5 O, E' Se) was obtained from 4 through the replacement a selenium atom P-Se(In) moiety by an oxygen atom, giving mixed-chalcogen complex. crystal structures 2 and exhibit central C4In2N6O2P4core with almost planar arrangement (mean deviation 0.019 0.042 A for 0.100 5), while C4In2N6S2P4...

Controlled hydrolysis of (Me)LGaCl2 ((Me)L = HC[(CMe)N(2,4,6-Me3C6H2)]2(-)) (1) in the presence a N-heterocyclic carbene, as HCl acceptor, led to unprecedented molecular galloxane dihydroxide [{(Me)LGa(OH)}2(μ-O)] (2) high yield. Compound 2 was used assembly heterobimetallic galloxanes with group 4 metals [{((Me)LGa)2(μ-O)}(μ-O)2{M(NR2)2}] (M Ti, R Me (6); M Zr (7), Hf (8), Et).

Unterdrückte Aggregation: Das Aluminoxanhydrogensulfid [{LAl(SH)}2(μ-O)] und die einzigartige sulfidverbrückte Verbindung [{LAl(SH)}2(μ-S)] wurden aus dem einfach zugänglichen Aluminiumdihydrid [LAlH2] (L=HC[(CMe)N(2,4,6-Me3C6H2)]2−) hergestellt. Wegen der cis-Konformation endständigen SH-Gruppen sind diese Verbindungen ideale Vorstufen für Synthese von Heterometallverbindungen. Supporting information for this article is available on the WWW under...

Abstract The alkaline earth metal complex [Mg{4,5‐(P(S)Ph 2 ) } tz} (thf) 4 ] ( and the bimetallic complexes, [ M {4,5‐(P(S)Ph (thf)] = Ca 3 ), Sr Ba 5 )], [SrI{4,5‐(P(S)Ph 6 [{BaI(4,5‐(P(S)Ph tz)} 7 were prepared in good yields from metathesis reactions of potassium salt 4,5‐bis(diphenylthiophosphoranyl)‐1,2,3‐triazole [H{4,5‐(P(S)Ph tz}] 1 I Ca, Sr, Ba), whereas tetrametallic magnesium hydroxide [Mg (μ‐OH){4,5‐(P(S)Ph 8 was obtained as hydrolysis product starting material (Mg n BuCl) . NMR...

Abstract Reactivity studies of aluminoxane hydroxide and hydrogensulfide [{ Me LAl(EH)} 2 (μ‐O)] { L = CH[CMe(NAr)] – (Ar 2,4,6‐Me 3 C 6 H ); E O ( 1 ), S )} with Group 4 amides led to the molecular heterobimetallic aluminoxanes [( LAlO) (μ‐O){M(NR ) }] [M Ti, R M Zr, Et 5 Hf, 7 )] sulfides LAlS) 8 9 10 11 12 13 )], respectively. The structural analyses these compounds reveal six‐membered inorganic cores that exhibit Al–E–M (E O, S; Hf) moieties. Compounds strong ··· (M transannular bonding,...

The novel M[(OPPh2)2N]2.nTHF (M = Sr (2), Ba (3)) complexes were prepared and characterized. Upon exposure to atmospheric oxygen, 2 3 transformed the dinuclear species Sr2-[(OPPh2)2N]4.2C3H6O3 (4) Ba(2)[(OPPh2)2N]4.2C4H8O3 (5), respectively. Compounds 4 5 contain coordinated carboxylic acids obtained from oxidative degradation of DME THF, respectively, which used as solvents for crystallization.

The syntheses and molecular structures of [M{N(SeP(i)Pr2)2-Se,Se'}2][M = Sn(2), Se(3)] are described, these complexes consist discrete, monomeric molecules featuring MSe4 cores that comprise true square-planar geometries.