99955-64-3Relevant academic research and scientific papers
Stepwise Metal-promoted Conversion of η2-CS2 into η2-SO. Synthesis and Crystal Structure of the Complex 2*HCONMe2
Bianchini, Claudio,Mealli, Carlo,Meli, Andrea,Sabat, Michal
, p. 1024 - 1025 (1985)
Nucleophilic attack by PEt3 at the carbon atom of the η2-CS2 ligand in (triphos)RhCl(η2-CS2) yields the η1-phosphoniodithiocarboxylate complex (triphos)RhCl(S2CPEt3), which reacts with dioxygen to
Novel reactions of the [BPh4]- salt of the bifunctional complex [(triphos)Rh(S2CO)]+ (triphos = MeC(CH2PPh2)3): One-electron reduction, cleavage of B-H and B-C bonds, and metathesis of CS2-like heteroallene molecules
Bianchini, Claudio,Meli, Andrea,Laschi, Franco,Vizza, Francesco,Zanello, Piero
, p. 227 - 233 (2008/10/08)
The redox properties of the Rh(III) dithiocarbonate complex [(triphos)Rh(S2CO)] [BPh4] ([1][BPh4]) have been studied in detail. One-electron reduction of [1][BPh4] gives the stable, paramagnetic Rh(II) derivative (triphos)Rh(S2CO) (4), which maintains the square-pyramidal (SQ) structure of the Rh(III) precursor as determined by ESR spectroscopy. The complex [1][BPh4] is able straightforwardly to cleave a B-H bond from BH3 to yield the hydride (triphos)RhH(S2CO) (5). In the presence of [Cu(PPh3)3] [ClO4] B-C bond cleavage occurs to give the σ-phenyl complex (triphos)RhPh(S2CO) (9). Compound [1][BPh4] reacts with CS2 or SCNR with evolution of COS and formation of trithiocarbonate [(triphos)Rh(S2CS)] [BPh4] (10) or dithiocarbonimidates [(triphos)Rh(S2CNR)] [BPh4] (R = Ph (11), Et (12)), respectively. Trithiocarbonate 10 and dithiocarbonimidates 11 and 12 are readily converted into each other with evolution of CS2 or SCNR by reaction with SCNR or CS2, respectively. The nature of the functionality that connects the two sulfur atoms of the 1,1-dithio ligands (i.e. >C=O, >C=S, or >C=NR) is of crucial importance in determining the electronic structure of the four-membered RhS2C metalla ring and, consequently, many physical and chemical properties of the complexes. The fluxional behavior in solution of a family of five-coordinate 1,1-dithio metal complexes of triphos is discussed on the basis of ESR and NMR techniques.
Chemical and electrochemical oxidation of the phosphoniodichalcogenoformate complexes (triphos)RhCl(X2CPEt3) (triphos = MeC(CH2PPh2)3; X = S, Se). Synthesis of metal dichalcogenocarbonates from O2 and phosphonium-betaine-like complexes. X-ray structure of [(triphos)Rh(S2CH(PEt3))](BPh4)2
Bianchini, Claudio,Meli, Andrea,Dapporto, Paolo,Tofanari, Anna,Zanello, Piero
, p. 3677 - 3682 (2008/10/08)
The phosphoniodichalcogenoformate complexes (triphos)RhCl(η1-X2CPEt3) (X = S, 1; Se, 2) are chemically or electrochemically oxidized to [(triphos)RhCl(η2-X2CPEt3)]2+ (triphos = MeC(CH2PPh2)3). These dications, which may add as many as two electrons to regenerate the starting compounds, react with EtOH, yielding octahedral phosphonium-betaine complexes of the formula [(triphos)RhCl(X2CH(PEt3))]+. The five-coordinate derivatives [(triphos)Rh(X2CH(PEt3))]2+ are obtained via chloride ligand elimination. Alternatively, the latter compounds can be prepared by the one-step reaction of 1 or 2 with HOSO2CF3 in the presence of NaBPh4. Methylation of 1 by MeOSO2CF3 gives the analogous complex containing the novel S2CMe(PEt3)- ligand. The structure of [(triphos)Rh(S2CH(PEt3))](BPh4)2 has been determined by X-ray methods. Crystal data: monoclinic, space group P21/n, with a = 18.433 (6) A?, b = 27.384 (8) A?, c = 16.229 (6) A?, β = 92.25 (4)°, and Z = 4. The structure was refined to an R factor of 0.075 (Rw = 0.075) for 4906 unique reflections. The rhodium atom is coordinated by the three phosphorus atoms of triphos and by the two sulfur atoms of the S2CH(PEt3)- ligand in a distorted-square-pyramidal environment. The neutral or cationic dichalcogenocarbonate complexes (triphos)RhCl(S2CO) and [(triphos)Rh(X2CO)]+ are obtained by reaction of O2 with solutions of [(triphos)RhCl(S2CH(PEt3))]+ and [(triphos)Rh(X2CY(PEt3))]2+ (Y = H, Me), respectively. Pathways to the formation of the products are proposed and discussed.
