71647-00-2

Upstream product

• 12092-47-6 di-μ-chloro-bis(1,5-cyclooctadiene)dirhodium 
• 2071-20-7 bis-diphenylphosphinomethane 
• 71647-01-3 Rh₂Cl(CO)2CO((C₆H₅)2PCH₂P(C₆H₅)2)2⁽¹⁺⁾*Cl^(1-)=[Rh₂Cl(CO)2CO((C₆H₅)2PCH₂P(C₆H₅)2)2]Cl 

Downstream Products

• 74507-89-4 Rh₂(CO)2(P(C₆H₅)2CH₂P(C₆H₅)2)2 
• 98535-90-1 {Rh2(μ-pyrazolato)(CO)2(μ-Ph2PCH2PPh2)2}Cl 
• 98535-92-3 {Rh2(μ-3,5-dimethylpyrazolato)(CO)2(μ-Ph2PCH2PPh2)2}Cl 
• 98767-10-3 bis-μ-{bis(diphenylphosphino)methane-P,P'}-μ-(3,5-dimethylpyrazolato-N,N')-bis{carbonylrhodium(I)} perchlorate 

Relevant academic research and scientific papers

Rhodium(I) macrocyclic and cage-like structures containing diphosphine bridging ligands

Abstract: Three series of rhodium organometallic complexes, mono-(1c, 2c, 5c, 6c), di-(1a-6a) and tetranuclear (1b, 5b, 6b), containing six different diphosphines 1,1′-bis(diphenylphosphino)methane or dppm (1), 1,2-bis(diphenylphosphino)ethane or dppe (2), 1,4-bis(diphenylphosphino)butane or dppb (3), bis(diphenylphosphino)acetylene or dppa (4), 1,2-bis(diphenylphosphino)benzene or dppbz (5) and 4,5-bis(diphenylphosphino)-9,9′-dimethylxanthene or xantphos (6) were successfully synthesised. These Rh(I) complexes were characterised by conventional techniques. The influence of the flexibility/rigidity of these P-donor ligands was carefully analysed, including their effect on both synthesis and catalysis. The luminescent properties of the dinuclear and tetranuclear complexes were investigated, and only those containing dppa, dppbz and xantphos displayed luminescence. Structures of the dinuclear complexes were modelled by using DFT methods in order to elucidate the most reasonable conformation. The different types of complexes were applied in the catalytic hydrogenation of (E)-4-phenylbut-3-en-2-one, showing high activity and similar catalytic behaviour. No cooperative effect could be inferred. Graphical Abstract: Three series of 1D, 2D and 3D rhodium complexes were successfully synthesised, and their emission properties were analysed. The large number of isomeric forms of the 2D were analysed by DFT methods. Their use in catalytic hydrogenation of (E)-4-phenylbut-3-en-2-one was studied showing high selectivity towards the formation of 4-phenylbutan-2-one.[Figure not available: see fulltext.]

Mono- and Bis-Bridged Ru-Rh Complexes. Preparation, Characterization, and Reactivity. X-ray Crystal Structure of RuRhH(Ph)(PhPCH2PPh2)(Ph2PCH2PPh2)(C8H12)*1/2PhMe and of RuHCl(Ph2PCH2PPh2)2*1/2PhMe

The reaction of RuCOD(dppm)2 (COD = cis,cis-1,5-cyclooctadiene, dppm = bis(diphenylphosphino)methane) with 2 affords Ru(CO)(COD)(dppm) and 2 at room temperature after ligand exchange.At 80 deg C two further products are obtained, Rh2Cl2(dppm)2 and RuRhCl(CO)3(dppm)2 (1), which is the main product if the reaction is performed under CO.A mechanism is proposed. 1 reacts with H2 to give RuRhH2Cl(CO)2(dppm)2 which can also be obtained from RuH2(dppm)2 and 2.The reaction of RuH2(dppm)2 with 2 leads to RuRhH2Cl(COD)(dppm)2 (3) which contains one bridging and one chelating dppm group. 3 does not react with C2H4, decomposes under H2, and reacts with CO to give 1 and with P(OMe)3 to give two isomers of RuHClP(OMe)3(dppm)2, 5 and 6, and RhH(POMe3)4.Similarly, the reaction of RuH2(dppm)2 with 2 produces RuIrH2Cl(COD)(dppm)2 (4) analogous to 3, but in this case some redistribution to RuHCl(dppm)2 is also observed.Finally, reduction of 3 with MeLi at 0 deg C leads to methane elimination and the formation of RuRhH(Ph)(PhPCH2PPh2)(dppm)(COD) (7) which contains a phosphido bridge between Ru and Rh and a trans hydrido phenyl environment for ruthenium. 7 reacts with CO to give RuRhH(Ph)(PhPCH2PPh2)(dppm)(CO)2 (8).Full spectroscopic characterization of the new complexes is described, viz., 1H, 13C, and 31P NMR and determination of the 103Rh resonance frequency.The crystal structures of RuHCl(dppm)2*1/2PhMe and of 7 are described.RuHCl(dppm)2*1/2PhMe: C2h5-P21/c; Z = 4; a = 10.138(2) Angstroem, b = 21.206(3) Angstroem, c = 22.066(3) Angstroem, β = 103.93(1) deg, V = 4604.4 Angstroem3, R = 0.046 for 2948 reflections with F02 > 3?(F02).RuRhHPh(PhPCH2PPh2) (COD)(dppm)*0.5PhMe: C2h5-P21/c; Z = 4; a = 15.985(3) Angstroem, b = 18.324(4) Angstroem, c = 19.496(4) Angstroem, β = 112.20(2) deg, V = 5287.2 Angstroem3, R = 0.034 for 4751 reflections with F02 > 4?(F02).

Molecular A-frames. Identification and characterization of the rhodium A-frame precursor complex bis(μ-hydrido)dicarbonylbis(bis(diphenylphosphino) methane)dirhodium, Rh2(μ-H)2(CO)2(dppm)2

The product of the borohydride reduction of Rh2Cl2(CO)2(dppm)2 has been reinvestigated and characterized as the dihydrido species Rh2(μ-H)2(CO)2(dppm)2. Under vacuum or N2, the complex rapidly loses H2 as it undergoes a first-order decomposition. The decomposition is inhibited by H2, and solutions of the complex under H2 are somewhat stabilized. Under D2 the rapid formation of HD is observed. Solutions of the complex under H2 react cleanly with various substrates. With HCl, the quantitative conversion to Rh2Cl2(CO)2(dppm)2 is observed. The complex reacts with HBr to form Rh2Br2(CO)2(dppm)2 and the new complex [Rh2(μ-H)(μ-CO)Br2(dppm)2]Br. Methyl iodide reacts with the complex to form 1 equiv of CH4 and the new complex Rh2(μ-H)(μ-I)(CO)2(dppm)2.

Binuclear rhodium complexes: Their chemistry with sulfur dioxide and the structure of [Rh2Cl2(μ-SO2)((C6H 5)2PCH2P(C6H5) 2)2]

The "A-frame" complex [Rh2(CO)2(μ-Cl)(DPM)2][B(C6H 5)4] (DPM = (C6H5)2PCH2P(C6H 5)2) undergoes a facile and reversible reaction with SO2 to yield [Rh2(CO)2(μ-Cl)(μ-SO2)(DPM) 2][B(C6H5)4]. Spectroscopic studies have shown that SO2 attack occurs directly at the bridging site of the "A-frame" complex. Treatment of a solution of the SO2 adduct with excess SO2 in the presence of chloride ion yields a second SO2 complex, [Rh2Cl2(μ-SO2)(DPM)2], the structure of which is reported. In the absence of chloride ion, formation of the second SO2 complex occurs in the presence of small amounts of [RhCl2(CO)2]- with the latter functioning as a chloride-transfer agent. Treatment of the second, SO2-bridged species with CO yields the complex [Rh2(CO)2(μ-CO)(μ-Cl)(DPM)2][Cl] which can then be readily converted in solution to the dicarbonyl species cis-[Rh2Cl2(CO)2(DPM)2]. The reaction of trans-[Rh2Cl2(CO)2(DPM)2] with SO2 has also been investigated and has been shown to occur by terminal SO2 attack, forcing the terminal carbonyl and chloro ligands on one Rh atom into the bridging positions. In solution this species then loses Cl- and rearranges to the complex [Rh2(CO)2(μ-Cl)(μ-SO2)(DPM) 2][Cl] which can yield [Rh2Cl2(μ-SO2)(DPM)2] by recoordination of Cl- and subsequent CO loss. The X-ray structural determination of [Rh2Cl2(μ-SO2)(DPM)2] shows this species to be a distorted "A-frame" complex with a symmetrically bridging SO2 ligand and terminal chloro ligands. The complex crystallizes in the space group C2h5-P21/c in a cell of dimensions a = 18.228 (1) A?, b = 13.526 (1) A?, c = 19.632 (2) A?, and β = 104.72 (1)° with Z = 4. On the basis of 5207 unique reflections, the structure was refined by full-matrix, least-squares techniques to agreement indices of R = 0.058 and Rw = 0.067. Some relevant metrical parameters are Rh-P(av) = 2.331 (9) A?, Rh-S(av) = 2.169 (2) A?, Rh-Cl(av) = 2.342 (2) A?, and Rh-S-Rh = 79.84 (7)°.