From MgBr via single-electron transfer (SET) to a paramagnetic Mg(II) compound and back to Mg(I): [MgBr(L(1))˙]2 and [K(thf)3]2[Mg2(L(1))2], L(1) = RN=C(Me)C(Me)=NR, R = 2,6-diisopropylphenyl.
نویسندگان
چکیده
Since Mg(+) ions are isoelectronic to Na atoms, an easy single electron transfer (SET) can be expected for MgBr. Even at 190 K, the radical MgBr (obtained via its sophisticated condensation) in a metastable solution transfers its electron to a diazadiene entity. A paramagnetic Mg(II) compound [MgBr(L(1))˙]2 (4; L(1) = DippN=C(Me)C(Me)=NDipp) is formed consisting of a singly reduced ligand. As shown by EPR investigations, dimeric 4 dissociates in ethereal solvents to two monomeric subunits. In addition, 4 can subsequently be reduced with potassium to furnish again a Mg(I) compound, namely [K(thf)3]2[Mg2(L(1))2] (3).
منابع مشابه
Chemistry of C - Trime th ylsil yl - Subs tituted Heterocarboranes . 17 . Syntheses , Structures , and Reactivities of Bent - Sandwich , do Zirconacarboranes of the " Carbons Adjacent " C 2 B 4 Carborane Systems
The reaction of ZrC4 with ~Z~SO-~~~-L~(THF)-~-N~(THF)-~-(S~M~~)-~-(R)-~,~-CZB~H~ (R = SiMe3, Me, H) in a benzeneA'HF solvent mixture produced l-Cl-l-(THF)-2,2'-(SiMe3)2-3,3'(R)~-4,4',5,5'-Li(THF)-l,l'-commo-Zr(2,3-C~B4H4)2 (R = SiMe3 (I), Me (111, H (11111, in 68%, 61%, and 59% yields, respectively. Compound I was found to be resistant to chloride substitution with common alkylating agents. Ins...
متن کاملReactions of α-diimine-aluminum complexes with sodium alkynides: versatile structures of aluminum σ-alkynide complexes.
Reaction of AlCl(3) with the monoanionic α-diimine ligand [NaL] yielded the complex [L˙(-)Al(III)Cl(2)(-)] (1, L = [(2,6-iPr(2)C(6)H(3))NC(Me)](2)), and subsequent reduction of by sodium metal afforded the mononuclear [L(2-)Al(III)Cl(-)(THF)] (2) and binuclear [L(2-)(THF)Al(II)-Al(II)(THF)L(2-)] (3). Compounds 2 and 3 exhibit interesting reactivities to sodium alkynides at room temperature. Tre...
متن کاملSynthesis and characterisation of magnesium complexes containing sterically demanding N,N'-bis(aryl)amidinate ligands.
Condensation reactions of carboxylic acids and anilines in the presence of polyphosphoric acid trimethylsilyl ester (PPSE) afforded a range of sterically demanding N,N'-bis(aryl)amidines, RN{C(R')}N(H)R [R = Mes (Mes = 2,4,6-trimethylphenyl), R' = Cy (Cy = cyclohexyl) L¹H; R = Dipp (Dipp = 2,6-diisopropylphenyl), R' = Cy L²H; R = Mes, R' = Ph L³H; R = Dipp, R' = Ph L⁴H; R = Mes, R' = Dmp (Dmp =...
متن کاملMany Mg-Mg bonds form the core of the Mg16Cp*8Br4K cluster anion: the key to a reassessment of the Grignard reagent (GR) formation process?
It caused a sensation eight years ago, when the first room temperature stable molecular compound with a Mg-Mg bond (LMgMgL, L = chelating ligand) containing magnesium in the oxidation state +1 was prepared. Here, we report the preparation of a [Mg16Cp*8Br4K]- cluster anion (Cp* = pentamethylcyclopentadiene) with 27 Mg-Mg bonds. It has been obtained through the reaction of KCp* with a metastable...
متن کاملSynthesis and rac-lactide ring-opening polymerisation studies of new alkaline earth tetrahydroborate complexes.
Reaction of K[HC(C(Me)NAr')(2)] (Ar' = 2,6-C(6)H(3)(i)Pr(2)) with Mg(BH(4))(2) afforded the pseudo four-coordinate tetrahydroborate complex Mg{HC(C(Me)NAr')(2)}(BH(4))(THF) (1). The corresponding reaction of Ca(BH(4))(2)(THF)(2) or Sr(BH(4))(2)(THF)(2) gave the pseudo five-coordinate analogues M{HC(C(Me)NAr')(2)}(BH(4))(THF)(2) (M = Ca (2) or Sr (3)). All three compounds 1-3 have been structura...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Chemical communications
دوره 50 99 شماره
صفحات -
تاریخ انتشار 2014