Synthesis and Physicochemical Characterization of Protonated and Deprotonated Forms in Heteroleptic Lanthanide(III) Porphyrinate Double-Deckers. X-ray Structure of Gd(III)H(oep)(tpp) at 298 and 21 K.

The synthesis, spectroscopic characterization, and electrochemical study of eleven heteroleptic and their corresponding homoleptic lanthanide sandwiches are reported. Studies in solution have been carried out in solvents of different basicity, in order to elucidate the equilibrium between the protonated and deprotonated form of these complexes. The investigated compounds are represented by the formulas Ln(III)H(oep)(tpp) and [Ln(III)(oep)(tpp)](-) corresponding to the protonated and deprotonated forms, respectively (in the case of heteroleptic), and the formulas Ln(III)H(tpp)(2) and [Ln(III)(tpp)(2)](-) (in the case of the homoleptic porphyrin double-deckers), where Ln Nd,.

Transition-Metal Derivatives of a Functionalized Cyclopentadienyl Ligand. 15. Synthesis and Structures of Amino Cyclopentadienyl Derivatives of Rhodium(I) and Rhodium(III) Including Water-Soluble Compounds.

The synthesis of monometallic rhodium(III) and rhodium(I) derivatives of dialkylamino-functionalized cyclopentadienyl using the corresponding cyclopentadiene as starting material is facilitated by the presence of the basic amino group. This procedure affords the chloro salts of the substituted rhodicinium cation [(eta(5)-C(5)H(4)(CH(2))(2)NMe(2)H)(2)Rh(III)](3+) ([1][Cl](3)) from the reaction of the [2-(dimethylamino)ethyl]cyclopentadiene with Na(3)Rh(III)Cl(6). 12H(2)O.

Transition-Metal Derivatives of the Cyclopentadienylphosphine Ligands. 11. Reactivity of the Dinuclear Bridged Rhodium(II) Complexes toward Nitrogen-Containing Ligands.

We report observations on the reactivity of the dinuclear bridged metal-metal-bonded carbonyl [Rh(II)(CO)(&mgr;-CpPPh(2))](2)(2+) (2(2+)) and of the bis(solvate) cations [Rh(II)(solv)(&mgr;-CpPPh(2))(2)](2)(2+) (3(2+)) with nitriles, amines and pyridine and in general with nitrosyl cation and nitrite anion. By reaction of nitriles and pyridine with 2(2+) we obtained monosubstituted [Rh(2)(CO)L(&mgr;-CpPPh(2))(2)](2+) (4(2+)) and disubstituted [Rh(L)(&mgr;-CpPPh(2))](2)(2+) (5(2+)) (L = MeCN, PhCN, pyridine). These complexes (5(2+)) were also obtained directly from 3(2+).