79272-85-8

Upstream product

• 79272-83-6 {Rh₂I₂(CO)((C₆H₅)2PCH₂P(C₆H₅)2)2} 
• 762-42-5 dimethyl acetylenedicarboxylate 
• 73680-38-3 {Rh₂I(CO)2((C₆H₅)2PCH₂P(C₆H₅)2)2}⁽¹⁺⁾*I^(1-)={Rh₂I(CO)2((C₆H₅)2PCH₂P(C₆H₅)2)2}I 
• 73680-37-2 {Rh₂Cl₂(CO)((C₆H₅)2PCH₂P(C₆H₅)2)2} 

Relevant academic research and scientific papers

Acetylene activation in binuclear rhodium complexes and the structure of [Rh2Cl2(μ-CO)(μ-CH3O2CC 2CO2CH3)(Ph2PCH2PPh 2)2]: A complex containing a bridging acetylene and a ketonic carbonyl ligand

trans-[RhCl(CO)(DPM)]2 and [Rh2Cl2(μ-CO)(DPM)2] react with DMA and HFB (DMA = CH3O2CC2CO2CH3; HFB = CF3C2CF3; DPM = Ph2PCH2PPh2), yielding the complexes [Rh2Cl2(μ-CO)(μ-acetylene)(DPM)2]. The bromo and iodo derivatives have also been prepared from [Rh2Br(CO)(μ-CO)(DPM)2][Br], [Rh2Br2(μ-CO)(DPM)2], [Rh2I(CO)(μ-CO)(DPM)2][I], and [Rh2I2(μ-CO)(DPM)2]. One member of this series, [Rh2Cl2(μ-CO)(μ-DMA)(DPM)2], has been structurally characterized by X-ray crystallography. This complex crystallizes in the space group P41212 with a = 15.021 (2) A?, c = 25.738 (5) A?, and Z = 4. On the basis of 4566 unique observed reflections, the structure has been refined to R = 0.049 and Rw = 0.066. The molecule contains an acetylene ligand bound to both metals as a cis-dimetalated olefin, a bridging ketonic carbonyl ligand, and no metal-metal bond. All parameters about the acetylenic carbon atoms suggest sp2 hybridization of these atoms. Similarly, the Rh-CO-Rh angle (116.0 (4)°) and the large metal-metal separation (3.3542 (9) A?) suggest that the carbonyl carbon atom is also sp2 hybridized and bound to the metals by two localized electron-pair bonds. The 13C NMR chemical shifts for these carbonyl carbons are at unusually high field compared to those for conventional carbonyl ligands, being more comparable to the values observed for organic carbonyl groups. The complex [Rh2Cl2(μ-CO)(DPM)2] catalyzes the cyclotrimerization of DMA but not its hydrogenation. In contrast, [Rh2Cl2(μ-CO)(DPM)2] catalyzes the hydrogenation of phenylacetylene to styrene but does not bring about its cyclotrimerization.