ChemInform Abstract: SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN‐SULFUR DONOR LIGANDS: THE CRYSTAL AND MOLECULAR STRUCTURE OF AQUA(1,7‐BIS(N‐METHYLBENZIMIDAZOL‐2′‐YL)‐2,6‐DITHIAHEPTANE)COPPER(II) PERCHLORATE

Abstract

Der durch i2 : l‐Kondensation von N‐Methyl‐o‐phenylendiamin und 2,6‐Dithiaheptan‐lJ‐dicarbonsäure in 50proz. Ausb. synthetisierte Titelligand bildet mit Cu(II)‐perchlorat einen Mono‐ und einen Dihydrat‐l :l‐Cu(ll)‐Komplex, die gegen‐ über einer Autoreduktion stabiler sind als jene des nicht‐methylienen Ligand‐ AnalogenDer Monohydtat‐Komplex wird durch eine Röntgenstrukturanalyse als 124 Aquo‐Komplex (I) (RG P21/n, Z=4) mit ionischen Perchlorat‐Ionen identifiziert, der eine Koordination zwischen trigonal‐bipyramidal und quadratisch‐planar besitzt.

Synthesis of Rhodium and Iridium Complexes Supported by Bis(indolylphosphino)silyl Pincer Ligation: Competitive N–H and C–H Bond Activation by an Ir(I) Species

“…Slight broadening with no coalescence of these resonances was observed upon heating a sample of 6a to 80 °C in toluene-d 8 . X-ray crystallographic data obtained for 6a (Figure 2; Table 1) further confirms the formulation of this complex and reveals a solid state structure (τ 5 = 0.29) 10 that is analogous to the related anilido and alkylamido Ir species 4a−c and 5a. The Ir− N3 distance of 1.982(2) Å is comparable to that observed for 5a (1.997( 5) Å) and somewhat shorter than that observed for the anilido derivatives ( Ir−N3 = 2.0336(19) Å for 4a, 2.019(4) for 4b, and 2.0315(15) Å for 4c).…”

“…Single crystal X-ray crystallographic data for 4a−c (Figure 2, Table 1) support their formulation. In each of 4a−c, the solid state structure indicates a five-coordinate metal center with coordination geometry similar to that of the hydrido-chloride precursor 2 (τ 5 = 0.088 for 4a, 0.28 for 4b, and 0.081 for 4c), 10 as well as related Cy-PSiP anilido hydride pincer complexes previously reported. 3n Acute Si−Ir−H1 angles are observed for all three structures, resulting in Interestingly, a minute amount of X-ray quality crystals obtained from a sample of crude 3a revealed an alternative structure (3a′, Figure 2) that features the NHPh group bound to Si, cleavage of a Si−N-indolyl bond, and transfer of the indolyl nitrogen donor to Rh to form a 4-membered Rh−N− C−P metallacycle (Figure 3).…”

“…The solid state structure of 5a (Figure 2; Table 1) was determined by use of X-ray crystallographic techniques and is comparable to the related anilido hydride complexes 4a−c (τ 5 = 0.0083). 10 The Ir−N3 distance of 1.997 (5) Å is in the range of those observed for the anilido derivatives and the geometry at the amido nitrogen is once again planar. Such examples of coordinatively unsaturated late metal alkylamido hydride complexes are exceedingly rare.…”

“…The highly reactive nature of 9a precluded its isolation, and as a result NMR data for this compound was obtained in situ. 1 ( fac-κ 3 -i Pr-PSiP Ind )IrH(κ 2 -P,C-o-C 6 H 4 PPh 2 ) (10). A solution of 2 (0.083 g, 0.11 mmol) in ca.…”

Electrocatalytic Hydrogen Production by a Nickel Complex Containing a Tetradentate Phosphine Ligand

“…Notably, 1 displays a square-pyramidal geometry in the solid state with an axial CH 3 CN ligand, with a τ 5 value of 0.02. 33 In contrast to 1, the related complex [Ni(tetraphos)(CH 3 CN)] 2+ (tetraphos = (R,R)-Ph 2 CH 2 CH 2 P(Ph)CH 2 CH 2 P(Ph)CH 2 CH 2 PPh 2 ) displays τ 5 values of 0.24 and 0.40 for two crystallographically independent molecules, 34 indicating a moderately to strongly distorted square pyramidal geometry. This structural difference is a consequence of the cyclic P 2 N 2 fragment in the P 4 N 2 backbone, which possesses a small P−Ni−P angle of 80.23(2)°.…”