[{Na⁺(thf)₂}₄(rubrene⁴⁻)]: Crystallization and Structure Determination of a Contact‐Ion Quintuple for the First π‐Hydrocarbon Tetraanion

Abstract

COMMUNrCATlONS P/ii..\. 1973. 2. 41; G. te Velde. E. J. Baerends, J. Compuf. P h w . 1992. 99, 84. Computational details: A local spin density approximation (S. H. Vosko, L. Wilk. M. h'usair, Cun. J Phw. 1980,58, 1200) was used in connection with the self-interaction correction ofStoll et al. (H. Stoll, C. M. E. Pavlidou, H. Preuss, 7/1ror. C / I I~. A r f u 1978.49, 143) and a gradient correction to the exchange part of the potcntial (A D. Becke, Phys. Rev A 1988, 38, 3098). Frozen core approximntion with the following Slater-type-orbital (STO) basis sets for the valence shell$. V. double.< for 3s. 3p. and 4s and triple-< for 3d, 0, N. and C, double.; for 7s and 2p: H double.; for Is. A set of auxiliary s. p, d, f. and g type STOa centered on the different atoms was used to fit the electronic density [15] a ) L. Noodleman.

A mixed valent heterometallic CuII/NaI coordination polymer with sodium–phenyl bonds

“…23 While these distances are longer than those typically observed in Na-Cp bonds (often as short as 2.5 Å), 24 the present separations are significantly shorter than the sum of the van der Waals radii of sodium and carbon (3.97 Å) confirming the presence of a sodium-phenyl bond. Indeed, sodium-benzene interactions of this type and in similar orientations have been predicted to have interaction energies of approximately −20 kcal mol −1 , 25 which in this case contribute to the stabilisation of the polymeric structure in the solid state.…”

“…Indeed, sodium-benzene interactions of this type and in similar orientations have been predicted to have interaction energies of approximately −20 kcal mol −1 , 25 which in this case contribute to the stabilisation of the polymeric structure in the solid state. While sodium-phenylene bonds have previously been observed, 23 they are uncommon in transition metal complexes.…”

Synthesis and Properties of Lanthanum- Pyrene Complexes—Structure of [(Cp*La)3(μ-Cl)3(thf)(μ-η2:η6:η6-C16H10)], the First Complex with a Pyrene Trianion

“…[9] Compound 2 can also be understood as a trinuclear complex with a phenanthrene bridge to which a noncoordinated double bond is attached; this view is supported by the strongly differing bond lengths C4 ± C5 and C11 ± C12 of 1.41 and 1.35 , respectively. The angles of the perpendiculars of the Cp*La and LaC 6 fragments are 128.138 and 128.568, respectively, for La1 and La2, and thus lie between those values for [{Cp 3 La} n ] [10] and {Cp* 2 La} systems. [11] These results indicate that the formation of 2, a compound with different coordination modes for La atoms bound in the complex, can be described by Equation (1).…”

“…The reduction of polyarenes with alkali metals in ethers leads to compounds in which ether-stabilized contact-ion pairs, [1] triples, [2] or even quintuples [3] occur. The known magnesium anthracene [4] and probably also some naphthalene complexes of europium, samarium, and ytterbium [5] are similarly built.…”

“…Since thiiranium compounds are known to be unstable in nucleophilic solvents, [2] we concentrated on the more stable aziridine analogues, which can be activated as alkylating reagents upon protonation of their ring nitrogen atom. [3] N-Adenosylaziridine (2) was synthesized by nucleophilic substitution of the tosylate group of 5'-deoxy-5'-tosyladenosine (tosyl Ts toluene-4-sulfonyl) with aziridine (Scheme 2). To test whether the cofactor analogue 2 serves as a cofactor for a Mtase we used the DNA Mtase from Thermus aquaticus (M´TaqI).…”