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The title complex [{PhS(tBuN)2}(Cl)Ge:→RhCl(cod)] (2) was synthesized by the reaction of three-coordinated chlorogermylene, [PhS(tBuN)2]GeCl (1), supported by a diimidosulfinate ligand with a half equivalent of [RhCl(cod)]2 in benzene. The molecular structure of 2 was determined by 1H and 13C NMR spectroscopies and single-crystal X-ray diffraction (SCXRD) analysis. The electronic property of germylene 1 was assessed by determining the Tolman electronic parameter of the corresponding cis-dicarbonyl Rh(I) complex, [{PhS(tBuN)2}(Cl)Ge:→RhCl(CO)2] (3), that was prepared by the treatment of 2 with carbon monoxide. [ABSTRACT FROM AUTHOR]

Three‐coordinated chlorogermylenes of the type [Ph2P(RN)2]GeCl (3: R=tBu; 4: R=Dip=2,6‐iPr2C6H3), which bear an N,N‐substituted iminophosphonamide ligand, were synthesized. The coordination behavior of 3 and 4 toward rhodium(I) complex was investigated. When 3 was treated with 1/2 of an equivalent of [RhCl(cod)]2 (cod=1,5‐cyclooctadiene), the corresponding chlorogermylene‐Rh(I) complex 5 was obtained as orange crystals. In contrast, the reaction of 4 with a half equivalent of [RhCl(cod)]2 under a CO atmosphere resulted in the formation of a five‐membered germarhodacycle 7. Compounds 3, 4, 5, and 7 were characterized using NMR spectroscopies and single‐crystal X‐ray diffraction. Complex 5 can be employed as a catalyst for the hydrosilylation and hydroboration reactions of diphenylacetylene, thus demonstrating the utility of germylene ligands comparable to those of NHCs in the major transition metal catalytic processes. [ABSTRACT FROM AUTHOR]

Dibenzyl zirconium(IV) complex (1), featuring an [OSSO]‐type bis(phenolate) ligand, served as a highly efficient pre‐catalyst for the polymerization of sterically bulky α‐olefins, such as vinyl cyclohexane (VCH) and 3‐methyl‐1‐butene (3‐MB). Upon activation with dried modified‐methylaluminoxane (dMMAO), the polymerization of VCH proceeded smoothly at 25°C to yield exclusively isotactic poly(VCH)s ([mm] >95%, Mw = 6500–19,400 g mol−1, PDI = 1.4), exhibiting good activity up to 924 g mmol(1)−1 h−1. The 1/dMMAO catalyst system also facilitated the polymerization of 3‐MB, producing colorless insoluble poly(3‐MB)s. DSC, TGA, and 13C CP‐MAS analyses showed the presence of highly isotactic microstructures in the resulting poly(3‐MB)s. Remarkably, the corresponding activity reached an impressive value of 898 g mmol(1)−1 h−1, surpassing that of previously reported homogeneous catalysts. [ABSTRACT FROM AUTHOR]

A novel α,β-unsaturated iminium salt (3) incorporated into a rigid dibenzobarrelene backbone was synthesized by heating N-(anthracen-9-ylmethyl)-2,6-diisopropylaniline (2) and 3-phenyl-2-propynal in THF in the presence of excess amounts of magnesium sulfate and 0.5 equivalents of an HBF4-Et2O complex. The molecular structure of 3 was characterized unambiguously by NMR spectroscopy and single-crystal X-ray diffraction (SCXRD) analyses. Compound 3 exhibits yellow luminescence in CH2Cl2 (λem = 516 nm) and in the solid state (λem = 517 nm) with relatively high to moderate quantum yields (ΦF(CH2Cl2) = 0.63; ΦF(solid) = 0.34). [ABSTRACT FROM AUTHOR]

The title complex {[Ph2P(tBuN)2](Cl)Si:->Fe(CO)4} (2) was synthesized via the reaction of chlorosilylene [Ph2P(tBuN)2]SiCl (1), supported by an iminophosphonamide ligand with Fe(CO)5 in THF. The molecular structure of 2 was fully characterized by NMR (1H, 13C, 29Si, and 31P) and IR spectroscopies, as well as single-crystal X-ray diffraction (SCXRD) analysis. In the SCXRD analysis of 2, the silylene ligand was located in the axial positions of the coordination sphere of the central iron atom and other sites were occupied by carbonyl ligands. [ABSTRACT FROM AUTHOR]