Synthesis, spectroscopy and structural characterization of five-coordinate, bis(aryldiazenido)technetium complexes and their protonation reactions. X-ray structure of [TcCl(PPh3)2(NNC6H4Br)2]

Group 7 ‘organohydrazide’ chemistry: classification of ligand type based on crystal structural data

“…As a result, the formal oxidation state of rhenium in these complexes should be assigned as ϩ3. The analogous Tc(NNC 6 H 4 Br) 2 (PPh 3 ) 2 Cl has also been synthesized and assigned as technetium() by Nicholson et al 10 The technetiumnitrogen bond length is 1.796(6) Å, and the nitrogen-nitrogen bond length is 1.229(9) Å. The bond lengths of all of these complexes demonstrate multiple bonding character throughout the diazenido unit.…”

Syntheses and characterization of phenyldiazenido and mixed phenyldiazenido–isocyanide complexes of rhenium. Crystal structure of [ReBr2(NNPh)2(PPh3)2]

“…three geometrical isomers, two of them with the diazenide ligands mutually cis (each of them trans to a bromide or to a phosphine, forms a or b, respectively) and the other one (form c) with the diazenide ligands in trans positions. However, the presence of isomers with different relative conformations of the phenyldiazenide ligands cannot be ruled out, as suggested 16 for [TcCl(NNC 6 H 4 OMe-4) 2 (PPh 3 ) 2 ] the 1 H NMR spectrum of which displays three resonances assigned to the methoxide protons. 2 For compounds 1 and 1Ј the 1 H NMR resonances (see Experimental section) of the phenyl protons of the phenyldiazenide ligands are observed as the expected multiplets at higher fields than those of free PPh 3 and BPh 4 Ϫ (the latter species in the case of 1Ј).…”

Reaktionen von Oxo-Rhenium(VII und V)-Verbindungen mit Thiobenzoylhydrazin. Kristall- und Molekülstrukturen von Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 und [Re(NHNC(S)Ph)(NHNHC(S)Ph)2]Cl · 1/3 C2H5OH · 1/3 H2O / Reactions of Oxorhenium(VII and V) Complexes with Thiobenzoylhydrazine. Crystal and Molecular Structures of Re(NHNC(S)Ph)3 · DMF, Re(NHNC(S)Ph)3 · OPPh3 and [Re(NHNC(S)Ph)(NHNHC(S)Ph)<

“…Die R henium koordinationssphäre weicht nur geringfügig von einer idealen tri gonal-prismatischen Symmetrie ab: in 1 ist die Ebene der drei Schwefelatome um durchschnittlich 1,1°, in 2 um 3,2° gegen die Ebene der Stickstoff atom e gedreht. M olybdän bildet eine zu 1 völlig analoge, aber nicht isotype Verbindung [12], "side on", wurden von uns in einer früheren Arbeit diskutiert [3], Vergleichende Zusammenstellungen sind auch in [8] und [11] enthalten. Welche F akto ren im einzelnen den Ligandentyp und seine Bin dung beeinflussen, ist noch nicht ganz klar.…”