51430-41-2

Upstream product

• 15668-64-1 tetracarbonyl(2,2'-bipyridine)molybdenum 
• 2071-20-7 bis-diphenylphosphinomethane 

Downstream Products

• 114024-81-6 Mo(II)Cl₂(CO)2(2,2'-bipyridine)(bis(diphenylphosphino)methane) 
• 69063-77-0 [RhCl(CO)((C₆H₅)2PCH₂P(C₆H₅)2)]2 
• 138844-46-9 {Mo(CO)3(C₁₀H₈N₂)(C₆H₅)2PCH₂P(C₆H₅)2(HgI)}⁽¹⁺⁾*{HgI₃}^(1-)={Mo(CO)3(C₁₀H₈N₂)(C₆H₅)2PCH₂P(C₆H₅)2(HgI)}{HgI₃} 

Relevant academic research and scientific papers

Calorimetric studies of the heats of protonation of the dangling phosphorus in η1-Ph2PCH2PPh2 complexes of chromium, molybdenum, and tungsten

Titration calorimetry has been used to determine the heats of protonation (ΔHHP) of M(CO)5(η1-dppm) (M = Cr, Mo, W) and fac-M(CO)3(Ndown curve signN)(η1-dppm) (M = Mo, Ndown curve signN = bipy, phen; M = W, Ndown curve signN = bipy) complexes with CF3SO3H in 1,2-dichloroethane solvent at 25.0°C. Spectroscopic studies show that protonation occurs at the uncoordinated phosphorus atom of the η1-coordinated dppm (Ph2PCH2PPh2) ligand. For dppm, its monoprotonated form (dppmH+), and these complexes, the basicity (ΔHHP) of the dangling phosphorus increases from -14.9 kcal/ mol to -23.1 kcal/mol in the order: dppmH+ 5(η1-dppm) 5(η1-dppm) 5(η1-dppm) 3(η2-bipy)(η1-dppm) 3(η2-phen)(η1-dppm) ≈ fac-W(CO)3(η2-bipy)(η1-dppm). In this series, H+ is more electron-withdrawing than M(CO)5 (M = Cr, Mo, W); Mo(CO)3(η2-phen) and W(CO)3(η2-bipy) actually enhance the basicity of the dangling phosphorus as compared with dppm itself. The basicity (ΔHHM) of fac-W(CO)3(η2-bipy)(PPh2Me), which protonates at the metal center to give a seven-coordinate complex, is -18.8 kcal/mol. Thus, the basicity of the dangling phosphorus atom in fac-W(CO)3(η2-bipy)(η1-dppm) is approximately 4.3 kcal/mol more basic than the metal center.

Molybdenum tricarbonyl complexes containing unidentate diphosphine. NMR study of fac-mer isomers and crystal structure of fac-Mo(CO)3(η2-phen)(η1-dppm)

The preparation of Mo(CO)3(η2-NN)(η1-dppm) (NN = 2,2'-bipyridyl (bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp); dppm = bis(diphenylphosphino)methane) by reactions of Mo(CO)4(η2-NN) with dppm have given a fac isomer or a fac-mer mixture depending on the nature of the NN ligand and on the reaction conditions. 1H, 13C and 31P NMR spectroscopy have been used for the characterization of fac and mer isomers.The X-ray structure of one of the phen derivative shows a fac configuration (monoclinic, P21/c, a 16.843(3), b 11.220(2),c 19.358(4) Angstroem, β 111.72(2) deg, V 3398 Angstroem3, Z = 4).A transformation in solution has been observed for both isomers, and the fac judged to be more stable than the mer isomer.

Substituted metal carbonyls III. Chromium, molybdenum and tungsten tricarbonyl complexes containing bipyridyl and a unidentate diphosphine: facile synthesis via trimethylamine N-oxide-induced decarbonylations

The ability of trimethylamine N-oxide as a chemical initiator for facile oxidative decarbonylation in metal carbonyls is manifested by the isolation of M(CO)3(η2-bipy)(η1-dppm) (where M = Cr, Mo, W; bipy = 2,2'-bipyridyl; dppm = bis(diphenylphosphino)-methane).The synthetic strategy and spectral (IR and 1H and 31P NMR) characterisations are presented and discussed.Syntheses of the well-known M(CO)4(η2-bipy) have also been modified to give high yields at ambient temperature.