84117-37-3

Upstream product

• 80502-54-1 cis-{Os(2,2'-bipyridine)2(CO)Cl}(PF₆) 
• 17084-13-8 potassium hexafluorophosphate 
• 16971-31-6 OsHCl(CO)(triphenylphosphine)₃ 
• 57288-05-8 [Os(2,2'-bypiridine)Cl₄] 
• 36007-23-5 mer-Os(PPh₃)3(CO)HCl 
• 56586-93-7 dichlorotris(triphenylphosphine)osmium(II) 

Downstream Products

• 106267-39-4 {Os(C₅H₄N)2(P(C₆H₅)3)2(CO)H₂}⁽²⁺⁾ 

Relevant academic research and scientific papers

Protonation of six-coordinate hydrido complexes of osmium(II). Examples of seven-coordination in osmium polypyridyl chemistry

The hydrido-osmium(II) complexes trans-[Os(chelate) (PPh3)2(CO)H](PF6) (chelate = 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, and 5,5′-dimethyl-2,2′-bipyridine) undergo protonation with trifluoromethanesulfonic acid (TFMSH) in CH2Cl2 or trifluoroacetic acid (TFAH) media to form the dihydrido complexes [Os(chelate)(PPh3)2(CO)H2]2+. Through the interpretation of a series of NMR spectral experiments involving 1H, 2H, and 31P nuclei, arguments are developed that implicate a pentagonal-bipyramidal solution structure for [Os(bpy)(PPh3)2(CO)H2]2+ in 10% TFMSH-90% TFAH (by volume) solution. The proposed structure, which has PPh3 ligands above and below the pentagonal plane but adjacent hydrido ligands, is consistent with a protonation mechanism involving the least molecular reorganization on going from octahedral trans-[Os(bpy)(PPh3)2(CO)H]+ to pentagonal-bipyramidal [Os(bpy)(PPh3)2(CO)H2]2+.

Hydrido carbonyl complexes of osmium(II) and ruthenium(II) containing polypyridyl ligands

Several different synthetic routes have been explored to produce hydrido complexes of Os(II) and Ru(II) containing polypyridyl ligands. The resulting complexes, the majority of which contain coordinated CO, are of three types: cis-[M(chelate)2(CO)H]+, trans-[Os(chelate)(PPh3)2(CO)H]+, and [Os(chelate)(diphos)(PR3)H]+ (where M = Ru or Os and chelate is, for example, 2,2′-bipyridine or 1,10-phenanthroline or a related ligand). The electronic, infrared, and NMR spectral properties of the complexes are discussed along with the redox properties of their ground and excited states. An important observation is that the hydride ligand endows the metal to ligand charge-transfer (MLCT) excited states of some of the complexes with strong reducing properties. The ground-state chemistry of the complexes is discussed especially with regard to their use as synthetic precursors to new, highly oxidizing, long-lived MLCT excited states of Os(II), e.g., [OsIII(bpy-.)(bpy)(CO)(CH3CH)]2+.