Transition Metal Diazoalkane Complexes. Synthesis, Structure, and Photochemistry of Rh[C(N_2)SiMe_3](PEt_3)_3

Reaction of RhCl(PR_3)_n (R = Me (n = 4), Et (n = 3)) and RhCl(CO)(PEt_3)_2 with (trimethylsilyl)diazomethyl lithium at −78 °C in ether yields the three complexes Rh[C(N_2)SiMe_3](PEt_3)_3 (1), Rh[C(N_2)SiMe_3](PMe_3)_4 (2), and Rh[C(N_2)SiMe_3](CO)(PEt_3)_2 (3). 2 could not be isolated as a solid at room temperature but 1 was precipitated as red crystals that were stable enough to be handled under argon. X-ray work on 1 reveals a tetrahedrally distorted square-planar geometry with the planar (trimethylsilyl)diazomethyl ligand roughly perpendicular to the P3RhC coordination plane. This distortion makes the PEt3 ligands nonequivalent in the crystal and produces an ABB‘X pattern in the solid-state ^(31)P NMR spectrum. Photolysis of Rh[C(N_2)SiMe_3](PEt_3)_3 leads quantitatively to the dimer [Rh{C(SiMe_3)(PEt_3)}(PEt_3)_2]_2 (4). The presence of the two ylide bridges and terminal phosphines is deduced from the COSY ^(31)P−^(31)P NMR spectrum. This photochemical reactivity suggests that the transient carbene (PEt_3)_3RhC̈(SiMe_3) is electrophilic, which is typical of a singlet carbene. We believe the singlet state is stabilized by the presence of the electron-rich low-spin Rh(PEt3)3 fragment. Reaction with ^nBuNC and ^tBuNC leads to stereo- and regioselective formation of a triazole that is σ bonded to the rhodium center. The X-ray structure of the ^tBuNC derivative Rh[CC(SiMe_3)N_2N^tBu](^tBuNC)_2(PEt_3) (5) shows a distorted square-planar geometry around Rh with the planar triazolato ligand roughly orthogonal to this plane. The probable reaction mechanism involves addition and substitution reactions of isocyanides at Rh followed by insertion into the Rh−C bond

Ethylenediamine- and propylenediaminediacetic acid derivatives as ligands for the "fac-[M(CO)3]+" core (M = Re, 99mTc)

The reaction of Re(CO)5Cl with o- or p-N-(nitrophenyl)ethylenediaminediacetic acid (H2L1, H2L2) and o- or p-N-(nitrophenyl)propylenediaminediacetic acid (H2L3, H2L4) in methanol leads to the formation of stable anionic [Et3NH][Re(CO)3(L)]·H2O complexes 1-4. These compounds have been characterized by means of IR, mass spectrometry, elemental analysis, NMR and conductimetry, as well as X-ray crystallography for 2 and 3. The [Re(CO)3]+ moiety is coordinated via the nitrogen of the iminodiacetic acid unit and two oxygens of monodentate carboxylate groups. In each case, the nitro group of the aromatic ring remains uncoordinated. The analogous technetium-99m complexes 1' and 3' were also prepared quantitatively by the reaction of H2L1 and H2L3, respectively, with the fac-[99mTc(CO)3(H2O)3]+ precursor in ethanol. The corresponding Re and 99mTc compounds were shown to possess the same structure by means of HPLC studies. The high affinity of these ligands for the Tc(I) or Re(I) core, coupled with the easiness of their derivatization (by reduction of the nitro group in amino group), implies that the utilization of this ligand system to develop target-specific radiopharmaceuticals for diagnosis and therapy is promising

Transition Metal Diazoalkane Complexes. Synthesis, Structure, and Photochemistry of Rh[C(N_2)SiMe_3](PEt_3)_3

Reaction of RhCl(PR_3)_n (R = Me (n = 4), Et (n = 3)) and RhCl(CO)(PEt_3)_2 with (trimethylsilyl)diazomethyl lithium at −78 °C in ether yields the three complexes Rh[C(N_2)SiMe_3](PEt_3)_3 (1), Rh[C(N_2)SiMe_3](PMe_3)_4 (2), and Rh[C(N_2)SiMe_3](CO)(PEt_3)_2 (3). 2 could not be isolated as a solid at room temperature but 1 was precipitated as red crystals that were stable enough to be handled under argon. X-ray work on 1 reveals a tetrahedrally distorted square-planar geometry with the planar (trimethylsilyl)diazomethyl ligand roughly perpendicular to the P3RhC coordination plane. This distortion makes the PEt3 ligands nonequivalent in the crystal and produces an ABB‘X pattern in the solid-state ^(31)P NMR spectrum. Photolysis of Rh[C(N_2)SiMe_3](PEt_3)_3 leads quantitatively to the dimer [Rh{C(SiMe_3)(PEt_3)}(PEt_3)_2]_2 (4). The presence of the two ylide bridges and terminal phosphines is deduced from the COSY ^(31)P−^(31)P NMR spectrum. This photochemical reactivity suggests that the transient carbene (PEt_3)_3RhC̈(SiMe_3) is electrophilic, which is typical of a singlet carbene. We believe the singlet state is stabilized by the presence of the electron-rich low-spin Rh(PEt3)3 fragment. Reaction with ^nBuNC and ^tBuNC leads to stereo- and regioselective formation of a triazole that is σ bonded to the rhodium center. The X-ray structure of the ^tBuNC derivative Rh[CC(SiMe_3)N_2N^tBu](^tBuNC)_2(PEt_3) (5) shows a distorted square-planar geometry around Rh with the planar triazolato ligand roughly orthogonal to this plane. The probable reaction mechanism involves addition and substitution reactions of isocyanides at Rh followed by insertion into the Rh−C bond

Synthesis and structural characterization of new oxorhenium and oxotechnetium complexes with XN2S-tetradentate semi-rigid ligands(X = O, S, N)

Twelve novel oxo-technetium and oxo-rhenium complexes based on N2S2-, N2SO- or N3S-tetradentate semi-rigid ligands have been synthesised and studied herein. By reacting the ligands with a slight excess of suitable [MO]3+ precursor (ReOCl3(PPh3)2 or [NBu4][99gTcOCl4]), the monoanionic complexes of general formula [MO(Ph–XN2S)]− could be easily produced in high yield. The complexes have been characterized by means of IR, electrospray mass spectrometry, elemental analysis, NMR and conductimetry. The crystal structures of [PPh4][ReO(Ph–ON2S)] 1b and [NBu4][99gTcO(Ph–ON2S)] 1c have been established. The [MO]3+ moiety was coordinated via the two deprotonated amide nitrogens, the oxygen and the terminal sulfur atoms in 1b and 1c. In both compounds, the ON2S coordination set is in the equatorial plane, and the complexes adopted a distorted square-pyramidal geometry with an axial oxo-group. The chemical and structural identity of the different prototypic complexes (rhenium, 99gTc complexes and their corresponding 99mTc radiocomplexes) have been also established by a comparative HPLC study

Étude photochimique des dibromo- et diiodotris (triméthylphosphine) nickel (II)

L’étude photochimique des deux complexes pentacoordinés Ni[P(CH3)3|3Br2 et Ni[P(CH3)3|3I2 a, en milieu anhydre et en présence de phosphine en excès, été suivie par speclrophotométrie électronique et par conductimétrie. Dans les deux cas un mécanisme photochimique identique de type SN1, conduisant à la formation de l’halogénure de pentakis (triméthyl- phosphine) nickelatc (II) a été proposé et confirmé

Synthèse et caractérisation de complexes de rhénium (V) et de technétium 99m à ligands phosphinoénolato et phosphinophénolato (application en radiopharmacie)

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF