Tetrylenes are Able to Discern between Isomeric Structures of Unsaturated Osmium(IV) Polyhydrides.

Hexahydride OsH(PPr) (1) releases H to form the isomeric tetrahydrides 2 a and 2 b of general formula OsH(PPr). Tetrylenes E{N(SiMe)} (E=Ge, Sn) are able to selectively trap these isomers distinguishing between them. Tetrylene Ge{N(SiMe)} catches 2 b to generate OsH{Ge[N(SiMe)]}(PPr) (3), which has a piano stool geometry, while Sn{N(SiMe)} captures 2 a to give OsH{Sn[N(SiMe)]}(PPr) (4) with the donor atoms defining a pentagonal bipyramid around the osmium center.

A Lead-μ-Tetrylide Complex with Osmium(IV) Terminal Components.

A bare lead atom is a σ-donor ligand capable of linearly bonding and stabilizing two units of a classical polyhydride complex, with a high-valent metal center. As a proof of concept, we have prepared and characterized the μ-tetrylide complex (PPr)HOs═Pb═OsH(PPr) in the reaction of OsH(PPr) with Pb{N(SiMe)}. Although the Pb-Os bonds exhibit electrostatic interaction, the main orbital interactions result from two dative σ bonds from the lead atom to the osmium centers.

-Pincers in Platinum Bimetallic Complexes: Influence of the Pincer and Bridging Ligands on the Metal-Metal Bond and the Photophysical Properties.

Precursors PtCl{κ--[py-CHMe-py]} (), PtCl{κ--[py-O-CH-O-py]} (), Pt(OH){κ--[py-CHMe-py]} (), and Pt(OH){κ--[py-O-CH-O-py]} () were used to prepare d-platinum bimetallic complexes. Precursors and react with AgBF and 7-azaindole (H) to give [Pt{κ--[py-CHMe-py]}{κ--[H]}]BF () and [Pt{κ--[py-O-CH-O-py]}{κ--[H]}]BF () and and with indolo[2,3-]indole (H) to generate Pt{κ--[H]}{κ--[py-CHMe-py]} () and Pt{κ--[H]}{κ--[py-O-CH-O-py]} (). Subsequent addition of and to - affords bimetallic derivatives [{Pt[κ--(py-CHMe-py)]}{μ--[]}]BF (), [{Pt[κ--(py-O-CH-O-py)]}{μ--[]}]BF (), and {Pt[κ--(py-CHMe-py)]}{μ--[]} ().

C-H, N-H, and O-H Bond Activations to Prepare Phosphorescent Hydride-Iridium(III)-Phosphine Emitters with Photocatalytic Achievement in C-C Coupling Reactions.

Complex IrH(PPr) () activates two different σ-bonds of 3-phenoxy-1-phenylisoquinoline, 2-(1-benzimidazol-2-yl)-6-phenylpyridine, 2-(1-indol-2-yl)-6-phenylpyridine, 2-(2-hydroxyphenyl)-6-phenylpyridine, -(2-hydroxyphenyl)-'-phenylimidazolylidene, and 1,3-di(2-pyridyl)-4,6-dimethylbenzene to give IrH{κ--[CH-isoqui-O-CH]}(PPr) (), IrH{κ--[NBzim-py-CH]}(PPr) (), IrH{κ--[Ind-py-CH]}(PPr) (), IrH{κ--[CH-py-CHO]}(PPr) (), IrH{κ--[CH-Im-CHO]}(PPr) (), and IrH{κ--[py-CHMe-CHN]}(PPr) (), respectively. The activations are sequential, with the second generally being the slowest. Accordingly, dihydride intermediates IrH{κ--[CH-isoqui-O-CH]}(PPr) (), IrH{κ--[NBzim-py-CH]}(PPr) (), IrH{κ--[Ind-py-CH]}(PPr) (), and IrH{κ--[py-CHMe-py]}(PPr) () were characterized spectroscopically.

Unequivocal Characterization of an Osmium Complex with a Terminal Sulfide Ligand and Its Transformation into Hydrosulfide and Methylsulfide.

Deprotonation of the thioamidate group of [OsH{κ-,-[NHC(CH)S]}(≡CPh)(IPr)(PPr)]OTf [; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf = CFSO] results in the release of acetonitrile and formation of the terminal sulfide complex OsH(S)(≡CPh)(IPr)(PPr) (), which has been transformed into the hydrosulfide [OsH(SH)(≡CPh)(IPr)(PPr)]OTf () and the methylsulfide [OsH(SMe)(≡CPh)(IPr)(PPr)]OTf () through protonation and methylation reactions, respectively. The structure, spectroscopic characteristics, and reactivity of these compounds are compared. Reactions of and with 2-hydroxypyridine and 2-mercaptopyridine afford [OsH{κ-,-[X-py]}(≡CPh)(IPr)(PPr)]OTf [X = O (), S()].