Oxidative addition/reductive elimination of aldehydes and ketones at rhodium. Synthesis and characterization of cis-hydrido acyl complexes of rhodium(III)

1987 ◽  
Vol 6 (11) ◽  
pp. 2453-2455 ◽  
Author(s):  
Claudio. Bianchini ◽  
Andrea. Meli ◽  
Maurizio. Peruzzini ◽  
Alberto. Vacca ◽  
Fabrizio. Zanobini
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Synthesis And Characterization ◽  
Acyl Complexes ◽  
Aldehydes And Ketones

Synthesis and study of platinum silylene complexes of the type (R3P)2Pt=SiMes2 (Mes = 2,4,6-trimethylphenyl)

2003 ◽  
Vol 81 (11) ◽  
pp. 1127-1136 ◽  
Author(s):  
Jay D Feldman ◽  
Gregory P Mitchell ◽  
Jörn-Oliver Nolte ◽  
T Don Tilley
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Synthesis And Characterization ◽  
Silylene Complexes

The synthesis and characterization of neutral platinum silylene complexes (R3P)2Pt=SiMes2 (R = i-Pr (1) or cyclohexyl (2), Mes = 2,4,6-trimethylphenyl) is reported. The dimesitylsilylene ligand in 2 is displaced by a number of ligands including phosphines, alkenes, alkynes, and O2. Complex 2 reacts with ROH substrates (R = H, Me, Et) to give (Cy3P)2Pt and Mes2Si(OR)(H) and with H2 to give trans-(Cy3P)2Pt(H)SiHMes2 (3). Reaction of H2SiMes2 with (Cy3P)2Pt gave cis-(Cy3P)2Pt(H)SiHMes2 (4). EXSY NMR experiments of 4 reveal that exchange of silicon and platinum hydrides occurs via reductive elimination – oxidative addition and not via a silylene intermediate.Key words: silylene, EXSY, platinum, hydride.

Dimethylplatinum(IV) Complexes With Cyanide: Thermal and Photoassisted Substitution Reactions, and Characterization of Products by N.M.R.

1987 ◽  
Vol 40 (9) ◽  
pp. 1565 ◽  
Author(s):  
TG Appleton ◽  
JR Hall ◽  
MA Williams
Keyword(s):  
Ultraviolet Irradiation ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Methyl Groups ◽  
Substitution Reactions ◽  
Aqueous Acid ◽  
Cyanide Ligands ◽  
Cis And Trans ◽  
Insoluble Precipitate

Reactions of cyanide with the dimethylplatinum (IV) complexes, [PtMe2(OH) (H20)1.5 n, [PtMe2Br2]n and fac-PtMe2Br(H2O)3+, have been studied, principally by 1H, 13C and 195Pt n.m.r. Cyanide rapidly displaces the ligands trans to the methyl groups. Subsequent reactions cis to the methyl groups occur more slowly with heating, or, for bromo complexes, on ultraviolet irradiation. These substitution reactions compete with reductive elimination of groups from the platinum(IV) compounds to produce platinum(II) products. All attempts to prepare solutions of fac-PtMe2(CN)(H2O)3+ were unsuccessful. Oxidative addition of ICN to cis-PtMe2( py )2 ( py = pyridine) gave PtMe2I(CN)( py )2, from which a solution of fac-PtMe2(CN)( MeOH )3+ in methanol could be obtained. Addition of water or aqueous acid to this solution gave a very insoluble precipitate of [PtMe2(CN)(OH)n. The cis and trans influences on Jpt -C and δC of the cyanide ligands have been evaluated.

Oxidative addition/reductive elimination of aldehydes and ketones at rhodium

1989 ◽  
Vol 8 (2) ◽  
pp. 337-345 ◽  
Author(s):  
Claudio. Bianchini ◽  
Andrea. Meli ◽  
Maurizio. Peruzzini ◽  
Jose A. Ramirez ◽  
Alberto. Vacca ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Aldehydes And Ketones

Synthesis and characterization of and stereoselective oxidative addition of chlorine or bromine to platinum complex, [NBu4][Pt(C6F5)2(C5H4NS)]

1993 ◽  
Vol 12 (11) ◽  
pp. 4368-4375 ◽  
Author(s):  
Juan Fornies ◽  
Consuelo Fortuno ◽  
Miguel A. Gomez ◽  
Babil Menjon ◽  
Eberhardt Herdtweck
Keyword(s):  
Platinum Complex ◽  
Oxidative Addition ◽  
Synthesis And Characterization

Synthesis and characterization of dimethyl- and dimethoxyphenylbis(N,N-dialkyldithiocarbamato)tellurium(IV) and chlorodimethyl- and chlorodimethoxyphenyl-(N,N-dialkyldithiocarbamato)tellurium(IV). Crystal structures of Me2Te[S2CNMe2]2 and (p-MeOC6H4)2Te[S2CNMe2]2

1993 ◽  
Vol 71 (1) ◽  
pp. 42-50 ◽  
Author(s):  
Jane H. E. Bailey ◽  
John E. Drake
Keyword(s):  
Nmr Spectroscopy ◽  
Crystal Structures ◽  
Variable Temperature ◽  
Reductive Elimination ◽  
Synthesis And Characterization ◽  
Space Group ◽  
Cell Parameters

The compounds Me2Te[S2CNR2]2, Me2TeCl[S2CNR2], (p-MeOC6H4)2Te[S2CNR2]2, and (p-MeOC6H4)2TeCl[S2CNR2], where R = Me, Et, have been prepared and characterised primarily by vibrational and NMR spectroscopy. Variable temperature NMR spectroscopy and qualitative time studies indicate that in solution the dimethoxyphenyltellurium derivatives undergo the reductive-elimination noted for analogous phenyl derivatives but the reductive-elimination does not occur with the dimethyl tellurium derivatives. The crystal structures of Me2Te[S2CNMe2]2, 1, and (p-MeOC6H4)2-Te[S2CNMe2]2, 5, were completed. The cell parameters for 1, which crystallizes as monoclinic in space group P21/n, are a = 13.550(2), b = 13.034(2), c = 17.854(2) Å, β = 106.61(1)°, V = 3021.6(7) Å3, Z = 8, R = 0.0368, and Rw = 0.0402 and for 5, which crystallizes as monoclinic in space group C2/c, are a = 35.36(1), b = 11.063(3), c = 12.778(3) Å, β = 96.16(3)°, V = 4963(3) Å3, Z = 8, R = 0.0627, and Rw = 0.0646.

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