Complexes of the (1R)-(+)-camphor azine diphosphines Z,Z-3,3 '-(Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x and Z,Z-3,3 '-(Ph2PC10H15)-C-x=N-N= (C10H15PPh2)-Ph-x (x = exo, n = endo) with Group 6 metal carbonyls: crystal structures of the ligands and fac-[W

摘要

Treatment of (1R)-(+)-camphor azine with 2 mole equivalents of butyllithium, followed by chlorodiphenyl-phosphine, gave the azine diphosphines Z,Z-3,3'-(Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x I and Z,Z-3,3'-(Ph2PC10H15)-C-x=N-N=(C10H15PPh2)-Ph-x II (x = exo, n = endo); the structures of these were determined by X-ray diffraction. On boiling an ethanol solution of the exo,exo-diphosphine II with sodium ethoxide or a propan-2-ol solution containing hydrazine hydrate and acetic acid the diphosphine isomerised to the corresponding exo,endo-diphosphine I. The corresponding diphosphine dioxides III and IV were prepared by treating I or II with H2O2, respectively. Treatment of I with [Mo(CO)(4)(nbd)](nbd = norbornadiene) or with [Mo(CO)(3)(cht)](cht = cydohepta-1,3,5-triene) gave fac-[Mo(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 1a. Treatment of I with [W(CO)(4)(nbd)] gave the tricarbonyltungsten(o) complex fac-[W(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 1b and the analogous mer complex mer-[W(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-x)] 2. Treatment of II with [W(CO)(6)] gave the mer,exo,endo tricarbonyl complex 2, and the fac,endo,endo complex fac-[W(CO)(3)((Ph2PC10H15)-C-n=N-N=(C10H15PPh2)-Ph-n)] 3. Treatment of II with [M(CO)(4)(nbd)] (M = Mo, W or Cr) gave mainly a complex of type fac-[M(CO)(3)((Ph2PC10H15)-C-x=N-N=(C10H15PPh2)-Ph-x)] (M = Mo 4a, W 4b or Cr 4c). The crystal structure of the tricarbonyltungsten(0) complex 4b was determined by X-ray diffraction and the chirality around tungsten shown to be C, i.e. clockwise. Treatment of 4b with 1 mole equivalent of bromine gave the tricarbonyltungsten(II) bromide salt [WBr(CO)(3)((Ph2PC10H15)-C-x=N-N=(C10H15PPh2)-Ph-x)]Br 5. Infrared, proton, phosphorus-31 and some carbon-13 NMR data are given. [References: 28]