The modular syntheses of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes and their homotrinuclear gold(I) complexes are reported. Choosing the arene core allows to fine-tune the exact oxidation potentials and thus to tailor the...

2,4,6-Tris(1-diphenylphosphanyl-1'-ferrocenylene)-1,3,5-triazine (1)c oordinates all three coinage metal(I) ions in a1 :1 tridentate coordination mode. The C 3 -symmetric coordination in both solids tate and solution is stabilisedb ya nu ncommon cation-p interaction between the triazine core and the metal cation. Intramolecular dynamic behaviour was observed by variable-temperature NMR spectroscopy.T he borane adduct of 1, 1BH 3 , displays four accessible oxidation states, suggesting complexes of 1 to be intriguing candidates for redox-switchable catalysis. Complexes 1Cu, 1Ag,a nd 1Au display a more complicated electrochemical behaviour,a nd the electrochemical mechanism was studied by temperatureresolved UV/Vis spectroelectrochemistry and chemical oxidation.Scheme1.Preparation of tris-phosphane 1 andits corresponding coinage metal complexes 1Cu, 1Ag,and 1Au.I solated yields are given in brackets. À-basedS E; arrowsd enote the startingp otentialand initial scan direction at 100 mV s À1 .The secondo fthreeconsecutively measured cycles is shownifnot noted otherwise. Bottomr ight: Equilibrium between two coordination isomersof1Cu in solution.

A facile two-step synthesis of bis(1-methylhydrazinyl)pyrimidine from pyridine-2-carbaldehyde and 2diphenylphosphanylbenzaldehyde gave access to the new asymmetric ligand 1. The phosphane selectively guides Pd II into the softer tridentate N,N,P pocket, yielding monometallic complex 2. A second reaction with a 3d transition metal complex precursor (groups 7 to 12) fills the vacant N,N,N pocket and thus provides a variety of heterobimetallic complexes of the type Pd II /M II (M = Mn (3), Fe (4), Co (5), Ni (6), Cu (7), Zn ( 8)). Single-crystal X-ray diffraction studies were performed for all complexes. The assembly of μ 2 -chlorido-bridged dimers was observed for complexes 5−7 in the solid state, while DOSY NMR experiments have shown that 5−7 are unbridged monomers in solution. As an exception, Fe II prefers to form the homoleptic meridional complex [Fe{PdCl(1)} 2 ](OTf) 4 (4). The electrochemical behavior and the effective magnetic moment in solution were investigated for all complexes by cyclic voltammetry and Evans method, respectively. Experimental UV/vis results were interpreted by performing TD-DFT calculations on 1, 2, and 3.

Two distorted square-planar RhI complexes (1 and 2) were obtained from [{RhCl(η4-cod)}2] and the respective P,N ligands.

The two highly flexible ligands 1,1'-bis(4-phospholanobutyl)ferrocene (5a) and 1,1'-bis(5-phospholanopentyl)ferrocene (5b) reacted with [PtCl2(cod)] (cod = 1,5-cyclooctadiene), [AuCl(tht)] (tht = tetrahydrothiophene) and [{RhCl(CO)2}2] to give the respective chelate complexes cis-[PtCl2(5a,b-κ(2)P,P')] (7a,b), [AuCl(5a,b-κ(2)P,P')] (8a,b) and trans-[RhCl(CO)(5b-κ(2)P,P')] (9b). Treatment of 5a,b with selenium gave the corresponding selenides 6a,b. All compounds have been fully characterised by NMR ((1)H, (13)C, (31)P) and IR spectroscopy and mass spectrometry. In addition, crystal structures of 6a, 7b, 8a,b and 9b were determined by X-ray crystallography. Furthermore, the rhodium-catalysed hydroformylation of 1-octene has been studied with ligand 5b.

Changing the aromatic core of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes has profound effects on their coordination behaviour towards gold(I). Depending on the arene (s-triazine, benzene, or trifluorobenzene), four different coordination modes can...

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Das Mercaptomethoxyphenol (I) reagiert mit B‐trichlorid zu dem 2‐Chlor‐ l ,3,2‐benzoxathiaborol (II).