Rhodium complexes phosphino

As terminated phosphino dendrimers, terminal diphosphino dendrimers (generations 1-3) react with Rh(acac) (COD) to give the expected diphosphino-rhodium complexes (Scheme 29). 

Another structurally well characterized rhodium complex containing the phosphino(stibino)methane ligand as a chelate is [H3Rh2(r 2-C)2CCF3)2 r 2-(z -Pr)2P-CH2-Sb(z-Bu)2 2]PF6.101... 

Figure 8.17. Molecular structure of the (amino)(phosphino)carbene rhodium complex XVdRH.

The diphenylphosphino group can be substituted by a phenylmercaptyl moiety [154] that would coordinate in chelate fashion to a rhodium centre, but only as a monodentate ligand (with the carbene) in the case of iridium. Interestingly, the rhodium complex, iso-structural to the P functionalised complex, is absolutely inactive in the hydrogenation of itaconate whereas the corresponding phosphino functionalised catalyst was reported to be highly active [154],... 

NOCkH, Benzoyl isocyanide, chromium complex, 26 32, 34, 35 NOPC25H21, Benzamide, 2-(diphenylphos-phino)-lV-phenyl-, 27 324 NOPC22H22, Benzamide, iV-(2-(diphenyl-phosphino)phenyl]-, 27 323 NO2QH5, 4-Pyridinecarboxylic acid, rhodium complex, 27 292... 

PRuC ,H, , Ruthenium(II), [2-(diphenyl-phosphino)phenyl-C P](T -hexamethyl-benzene)hydrido-, 36 182 PSC2H7, Phosphine sulfide, dimethyl-, and manganese complex, 26 162 PS3C7H , Phosphonium, (dithiocarboxy)-triethyl-, rhodium complex,... 

Asymmetric hydroboration of norbornene (27) is a synthetically useful transformation forming optically active norbornanol (28) which is an important chiral synthon. The catalytic enantioselective hydroboration with catecholborane was examined using rhodium complexes coordinated with several chiral phosphine ligands (Scheme 7 and Table 4) [14,15,17,23,24,27]. For this reaction, DIOP (10) and its derivatives 21 and 22, which are modified on the diphenyl-phosphino group, are more enantioselective Hgands than BINAP (7) or chira-phos (9). The highest enantioselectivity was observed in the reaction at -25 °C... 

CigHjjP, Phosphine, tricyclohexyl-, iron complex, 26 61, 28 171, 176, 29 154 molybdenum complex, 27 3, 13 nickel complexes, 26 205, 206 palladium and platinum complexes, 28 114, 116, 28 114, 116 platinum complex, 28 130 rhodium complex, 27 291 tungsten complex, 27 6 C H 70P, Benzenemethanol, 2-(diphenyl-phosphino)-, manganese complex, 26 169... 

NOCgHj, Benzoyl isocyanide, chromium complex, 26 32,34,35 N0C,3H,3, Formanide, N-(l-(l-naphthal-enyl)ethyll-, rhenium complex, 29 217 NOPCjsHjj, Benzamide. 2-(diphenylphos-phino)-N-phenyl-, 27 324 NOPCjjHjj, Benzamide, Af-[2-(diphenyl-phosphino)phenyl]-, 27 323 NO2CH3, Methane, nitro-, antimony complex, 29 113 cobalt complex, 29 114 NOjCjHj, 4-Pyridinecarboxylic acid, rhodium complex, 27 292 NO2P2C3JH33, Phosphorus(l-t-), p-nitrido-bis(triphenyl-, acetate, 27 296 NO2SC3H7, L-Cysteine, molybdenum complex, 29 255,258... 

The preparation of (silyloxy)rhodium complexes of the type [Rh2(fi-OSiR3)2(Ti -COD)2l (R = Me, Ph), which could serve as models of rhodium complexes bound to silica, has been reported238. The synthesis of the water-soluble complex [Rh(Ti -COD)(DPPETS)]+[Cl]" (DPPETS = l,2-bis bis(m-sodiosulfonatophenyl)phosphino ethane) has been reported and its catalytic activity in two-phase hydroformylation reactions investigated. The mechanism of the homogeneous reduction of (Z)-a-acetamido and (Z)-a-benzamidocinnamic acid methyl ester and a-acetamidoacrylic acid methyl ester in an organic-water medium in the presence of catalysts derived from [Rh2(lt-Cl)2(Ti -COD)2] and chiral sulphonated phosphines has been investigated W. ... 

P3C4,H3 , Phosphine, [2>[(diphenyl phosphino)methyl]-2-methyl-l,3-pTopanediyl]bis(diphenylK rhodium complex, 27 287... 

The preparation of chiral compounds by catalytic asymmetric hydrogenation is now well established. This year has again seen several reports on both the synthesis of and mechanistic studies on such systems, optical yields of 90% being achieved with a variety of catalysts. One such system which is worthy of note is the rhodium complex of the extremely simple chiral ligand (i )-l,2-bis(diphenyl-phosphino)propane [(i )-prophos] (7). This system is an efficient hydro-... 

Inoguchi K, Achiwa K. Efficient asymmetric hydrogenation of (Z)-2-acetamidocinnamic acid catalyzed by the rhodium complex of modified Af-benzyl-(3/f-, 4/f-)-3,4-bis(diphenyl-phosphino)pyrrolidine (DegPhos). Chem. Pharm. Bull. 1990 38 818-820. 

Rhodium and ruthenium complexes have also been studied as effective catalysts. Rh(diphos)2Cl [diphos = l,2-bis(diphenyl-phosphino)ethane] catalyzed the electroreduction of C02 in acetonitrile solution.146 Formate was produced at current efficiencies of ca. 20-40% in dry acetonitrile at ca. -1.5 V (versus Ag wire). It was suggested that acetonitrile itself was the source of the hydrogen atom and that formation of the hydride HRh(diphos)2 as an active intermediate was involved. Rh(bpy)3Cl3, which had been used as a catalyst for the two-electron reduction of NAD+ (nicotinamide adenine dinucleotide) to NADH by Wienkamp and Steckhan,147 has also acted as a catalyst for C02 reduction in aqueous solutions (0.1 M TEAP) at -1.1 V versus SCE using Hg, Pb, In, graphite, and n-Ti02 electrodes.148 Formate was the main... 

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