The dichloromethane induced fragmentation of ferrocenylmethyldimethylamine. Mechanistic aspects and crystallographic and electrochemical investigation of the (FcCH2)2NMe2+ and FcCH2NMe2H+ ions1

Ferrocenylmethyldimethylamine, FcCH2NMe2, reacts with CH2Cl2 in either the presence or absence of non-coordinating counterions to give equimolar amounts of the bis(ferrocenylmethyl)dimethyl ammonium salts (FcCH2)2NMe2+X− (X−=PF6−, SbF6−, BPh4− or Cl−, 1a–d) and the corresponding protonated ammonium salts FcCH2NMe2H+ which have been isolated as the SbF6− and Cl− salts 2b,d. The reaction proceeds via fragmentation of an intermediate quaternary chloromethylated ammonium ion to chloromethylferrocene, FcCH2Cl, and dimethyliminium chloride NMe2CH2+Cl−. The parent amine acts as a nucleophile toward FcCH2Cl to give 1a–d and as a base toward NMe2CH2+ to give FcCH2NMe2H+, NMe2H and (Me2N)2CH2. The FcCH2Cl intermediate is intercepted by NEt3 while KCN or LiH do not successfully compete with FcCH2NMe2. A new, non-toxic, selective, high-yield route to 1d is also presented. Electrochemistry and UV–vis spectroelectrochemistry reveal, that the two identical redox centers in 1a–d are essentially non-interacting. Individual E1/2 values have been determined for different solvents by digital simulation. The corresponding ferrocenium salts were prepared by either chemical or electrochemical means and accordingly characterized. Our studies are augmented by X-ray structure analyses of 1b, 1d and 2d. 1d contains three different cation conformers and four molecules of water per unit cell. The latter are hydrogen bonded to the chloride counterions to form one-dimensional infinite chains parallel to the a axis

Mercury chalcogenolates of a ligand having both sterically more bulkier and intramolecularly coordinating features: first isolation of a novel air stable mercury tellurolate

Synthesis and characterization of stable monomeric mercury selenolate (9) and the novel air stable mercury tellurolate (10) incorporating [2-[1-(3,5 dimethylphenyl)-2-naphthyl]-4,5-dihydro-4,4-dimethyloxazole], containing both sterically more demanding and intramolecularly coordinating groups have been described here. These complexes were prepared in good yields by oxidative addition of mercury metal to the corresponding dichalcogenides in methanol. FT-IR, multinuclear (<SUP>1</SUP>H, <SUP>13</SUP>C, <SUP>77</SUP>Se and <SUP>125</SUP>Te) NMR, thermal analysis and mass spectrometric techniques were used to characterize these complexes. The complex 9 was structurally characterized by single-crystal X-ray diffraction analysis

Synthesis of a metallophilic metallamacrocycle: a Hg<SUP>II</SUP>···Cu<SUP>I</SUP>···Hg<SUP>II</SUP>···Hg<SUP>II</SUP>···Cu<SUP>I</SUP>···Hg<SUP>II</SUP> interaction

Complexation of a CuI ion in a mercuramacrocycle demonstrates the potential of metal-metal interactions in a preorganized system to trap metal ions. The molecular structure of the CuI complex is presented and shows Hg&#183;&#183;&#183;Cu heterometallic and Hg&#183;&#183;&#183;Hg homometallic d10&#183;&#183;&#183;d10 interactions (see figure)

Cyclo-As₈ as Complex Ligand

The arsenic analogue of cyclooctatetraenecyclo-As8 can be stabilized as a strongly distorted, puckered eight-membered ring in a complex of niobium (1; each Nb atom also bears a 1,3-di-tert-butylcyclopentadienyl ligand). Complex 1 reacts with [Cr(CO)5(thf)] to form a trinuclear Nb2Cr cluster

Coordinative stabilization of a phosphido-phosphinidene ligand

The phosphido-phosphinidene coordination mode Cof a P2 ligand has been realized in the trinuclear complex [(TaL)3(P4)(P2)]2(L = 1,3-But2C5H3); structural proof was obtained by X-ray structure determination of the [(TaL)3(P4{Fe(CO)4}MP2)] derivative 3

Synthesis of diaryl selenides using the in situ reagent SeCl<SUB>2</SUB>

Reactions of in situ prepared SeCl<SUB>2</SUB> with Grignard reagents (prepared from bromobenzene, o-tolyl bromide, 2,6-dimethyl-4-tert-butyl-1-bromobenzene, and 1-bromo-2-methylnaphthalene) and dilithiated benzamides (prepared from N-phenyl, N-cyclohexyl, and N-isopropyl benzamide) are described