Facile interconversion of mesitylcopper into a CuMes-Cubis(amidinate) triangle and a tetracuprous Möbius strip.

A new flexible bis(amidine) ligand featuring two additional N-donor groups incorporates a defined [CuMesCu] fragment from mesitylcopper into a triangular cluster with a reactive organometallic coordination site. Subtle changes to the reaction protocol result in the formation of an intertwined tetracuprous arrangement that adopts the shape of a Möbius strip.

Syntheses, homeomorphic and configurational isomerizations, and structures of macrocyclic aliphatic dibridgehead diphosphines; molecules that turn themselves inside out.

The diphosphine complexes - or -[upper bond 1 start]PtCl(P((CH) )P[upper bond 1 end]) ( = b/12, c/14, d/16, e/18) are demetalated by MC[triple bond, length as m-dash]X nucleophiles to give the title compounds (P((CH) ))P (3b-e, 91-71%). These "empty cages" react with PdCl or PtCl sources to afford -[upper bond 1 start]MCl(P((CH) )P[upper bond 1 end]). Low temperature P NMR spectra of 3b and c show two rapidly equilibrating species (3b, 86 : 14; 3c, 97 : 3), assigned based upon computational data to , (major) and , isomers.

Non-conventional hydrogen bonding and dispersion forces that support embedding mesitylgold into a tailored bis(amidine) framework.

A bis(amidine) ligand operates as a molecular lock for two AuMes fragments. The resulting complex retains a flexible double macrocycle with two non-conventional N-H⋯C hydrogen bonds and distinct intramolecular dispersion forces. Instead of unfolding of the double-ring structure through bond rupture in solution, a conformational ring inversion is observed.

Ethylene-Bridged Hexadentate Bis(amidines) and Bis(amidinates) with Variable Binding Sites.

Hexadentate bis(amidines) form versatile networks of hydrogen bonds both in solid state and solution, as revealed by X-ray crystallography, IR, and NMR spectroscopy. Moreover, the corresponding bis(amidinates) produce blue and green emissions in THF solution. Tethered tetradentate bis(amidines) have emerged in coordination chemistry, enantioselective catalysis, as building blocks for polyfunctional heterocycles, and in photoluminescent materials.

Linear Copper Complex Arrays as Versatile Molecular Strings: Syntheses, Structures, Luminescence, and Magnetism.

The defined linear arrangement of metal atoms in discrete coordination complexes or polymers is still one of the most intriguing challenges in synthetic chemistry. These chain arrangements are of fundamental importance, because of their potential applications as molecular wires and single molecule magnets (SMM) in microelectronic devices on a molecular scale. Oligonuclear Group 11 metal complexes with suitable bridging ligands, specifically those that are based on copper as the first choice of a cheap precursor coinage metal, are of particular interest in this regard.

Non-metal-templated approaches to bis(borane) derivatives of macrocyclic dibridgehead diphosphines via alkene metathesis.

Two routes to the title compounds are evaluated. First, a ca. 0.

Homeomorphic Isomerization as a Design Element in Container Molecules; Binding, Displacement, and Selective Transport of MCl Species (M = Pt, Pd, Ni).

The dibridgehead diphosphine ((CH)) P (1) can rapidly turn inside-out (homeomorphic isomerization) to give a mixture of in,in and out,out isomers. The exo directed lone pairs in the latter are able to scavenge Lewis acidic MCl; cagelike adducts of the in,in isomer, trans- Cl(P((CH)) P) (M = 2/Pt, 3/Pd, 4/Ni), then form. The NiCl unit in 4 may be replaced by PtCl or PdCl, but 2 and 3 do not give similar substitutions.

Highly Luminescent Linear Complex Arrays of up to Eight Cuprous Centers.

Linearly arranged metal atoms that are embedded in discrete molecules have fascinated scientists across various disciplines for decades; this is attributed to their potential use in microelectronic devices on a submicroscopic scale. Luminescent oligonuclear Group 11 metal complexes are of particular interest for applications in molecular light-emitting devices. Herein, we describe the synthesis and characterization of a rare, homoleptic, and neutral linearly arranged tetranuclear Cu(I) complex that is helically bent, thus representing a molecular coil in the solid state.

Steric control of the in/out sense of bridgehead substituents in macrobicyclic compounds: isolation of new "crossed chain" variants of in/out isomers.

Isomers of the cage like dibridgehead diphosphine P((CH2)14)3P (1) are treated with Ph3PAu(2,6-C6H3(Trip)2) (2 equiv.; Trip = 2,4,6-C6H2(iPr)3). With out,out-1, workup gives out,out-1·(Au(2,6-C6H3(Trip)2))2 (46%), as confirmed by a crystal structure.

Gyroscope-like molecules consisting of PdX₂/PtX₂ rotators within three-spoke dibridgehead diphosphine stators: syntheses, substitution reactions, structures, and dynamic properties.

Threefold intramolecular ring-closing metatheses of trans-[MCl2(P{(CH2)(m)CH=CH2}3)2] are effected with Grubbs' catalyst. Following hydrogenation catalyzed by [RhCl(PPh3)3], the title complexes trans-[MCl2(P((CH2)n)3P)] (n=2m+2; M/n=Pt/14, 4 c; Pt/16, 4 d; Pt/18, 4 e; Pd/14, 5 c; Pd/18, 5 e) and sometimes isomers partly derived from intraligand metathesis, trans-[MCl2{P(CH2)n(CH2)n}P(CH2)n)] (4'c-e, 5'e), are isolated. These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58-99%).

Oligonuclear homoleptic copper(I) pyrazolates with multinucleating ligand scaffolds: high structural diversity in solid-state and solution.

The synthesis of three pyrazole-based, potentially binucleating ligands 3,5-bis(R(1)N(CH(3))CH(2))-4-R(2)pyrazole (L(1)H: R(1) = pyridyl-2-methyl-, R(2) = Ph; L(2)H: R(1) = 8-quinolyl-, R(2) = H; L(3)H: R(1) = 8-quinolyl-, R(2) = Ph) is described. Reaction of L(1-3)H with 1 equiv. of mesitylcopper affords oligonuclear homoleptic complexes of the type [CuL](n) (1-3).

An unusually stable octanuclear sigma-mesityl-bridged mu4-oxo-copper(I) complex encapsulated by a pyrazolate-based compartmental ligand scaffold.

A new compartmental pyrazole-derived chelating ligand, four equivalents of mesitylcopper and stoichiometric amounts of dioxygen lead to the formation of a remarkably stable organometallic framework that can be described as a heteroleptic O-centered cuprate anion [(MesCu(I))(4)(mu(4)-O)](2-) linked via sigma-mesityl-bridges to two surrounding binuclear Cu(I)-pyrazolate clamps.