Complexes of an azine diphosphine with Group 6 metal carbonyls: crystal structures of Z,Z-PPh2CH2C(But)N–NC(But)CH2PPh2and [Mo(CO)3(E,Z-PPh2CH2C(But)N–N(But)CCH2PPh2)]
- 1 January 1992
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 9,p. 1469-1475
- https://doi.org/10.1039/dt9920001469
Abstract
Treatment of the azine MeC(But)NNC(But)Me with 2 equivalents of LiBun, followed by 2 equivalents of PPh2Cl, gives the azine diphosphine Z,Z-PPh2CH2C(But)N–N(But)CCH2PPh21. This new diphosphine was treated with H2O2 to give the corresponding diphosphine dioxide 2a and with monoclinic sulfur to give the diphosphine disulfide 2b. Treatment of [M(CO)3(η6-cht)](cht = cyclohepta-2,4,6-triene) with 1 gave the metal tricarbonyl fac-[[graphic omitted]Ph2}](M = Mo, 3a; W, 3b; or Cr, 3c) in which the azine diphosphine is bonded in the E,Z configuration. Complexes 3a and 3b were also made by treating the corresponding metal hexacarbonyls with the azine diphosphine 1. Treatment of [M(CO)4(nbd)](M = Mo, W, or Cr; nbd = norbornadiene) with 1 gave the tetracarbonyl complexes [[graphic omitted]Ph2}]4 with the E,Z-azine diphosphine acting as a bidentate ligand. On heating, these tetracarbonyl complexes 4 were converted into the tricarbonyl complexes 3. Treatment of either 3a or 4a with 1 mol equivalent of bromine gave the neutral molybdenum(II) complex [[graphic omitted]Ph2}]5, whereas the tungsten complexes 3b and 4b with bromine gave the cation [[graphic omitted]Ph2}]+ isolated as its BPh4 – salt 6. Proton, 13C-{1H} and 31P-{1H} NMR and infrared data are given. Crystals of 1 are monoclinic, space group P21/n, with a= 1667.2(2), b= 572.85(6), c= 1811.0(2) pm, β= 111.595(8)° and Z= 2; final R factor 0.0519 for 2049 observed reflections. Crystals of 3a are monoclinic, space group P21/n, with a= 985.7(1), b= 1870.2(2), c= 2220.8(2) pm, β= 93.71(1)° and Z= 4, final R factor 0.0354 for 5219 observed reflections.Keywords
This publication has 10 references indexed in Scilit:
- 3-Diphenylphosphino-(1R)-(+)-camphor dimethylhydrazone complexes with platinum(II) and palladium(II)J. Chem. Soc., Dalton Trans., 1992
- 3-Diphenylphosphino-(1R)-(+)-camphor dimethylhydrazone and its complexes with Group 6 metal carbonyls: crystal structures of the hydrazone and [Mo(CO)4(PPh2C10H15NNMe2)]J. Chem. Soc., Dalton Trans., 1991
- Faster data collection without loss of precision. An extension of the learnt profile methodActa Crystallographica Section A, 1981
- Geometrical isomers of the capped octahedron in the solid state. Crystal and molecular structure of dibromodicarbonyltris(dimethyl-phenylphosphine) molybdenum(II)–acetone (1/1)J. Chem. Soc., Dalton Trans., 1977
- A novel rearrangement of ketazine dianion: New synthetic route to pyrroles and tetrahydropyridazinesTetrahedron Letters, 1976
- Aktivierung organischer Verbindungen durch Einführung von Übergangsmetallatomen, VII1) Verknüpfung von Ketazinen über C‐Atome via KupferorganyleEuropean Journal of Organic Chemistry, 1970
- syn‐anti Isomerizations and rearrangementsPublished by Wiley ,1970
- Some tertiary phosphine and tertiary arsine complexes of molybdenum-(II), molybdenum(IV), tungsten(II), and tungsten(IV)J. Chem. Soc. A, 1970
- C-alkylations of ketone or aldehyde phenylhydrazones, oximes, and azines having .alpha. hydrogen through 1,4- or 1,6-dianionsJournal of the American Chemical Society, 1969
- CCLXXX.—The action of hydrazines on semicarbazones. Part IIIJournal of the Chemical Society, 1927